Polycarbonate-polyorganosiloxane copolymer, polycarbonate resin composition including same, and molded product thereof

ABSTRACT

Provided is a polycarbonate-polyorganosiloxane copolymer including polycarbonate blocks (A-1) each formed of a specific repeating unit and polyorganosiloxane blocks (A-2) each containing a specific repeating unit, wherein the polycarbonate-polyorganosiloxane copolymer satisfies the following expression (F1a):
 
15≤ wM 1  (F1a)
 
wherein wM1 represents the average content of the polyorganosiloxane blocks (A-2) in polycarbonate-polyorganosiloxane copolymers each having a molecular weight determined by using a polycarbonate as a conversion reference of from 56,000 or more to 200,000 or less among polycarbonate-polyorganosiloxane copolymers obtained through the separation of the polycarbonate-polyorganosiloxane copolymer by gel permeation chromatography.

RELATED APPLICATIONS

The present application claims priority under 37 U.S.C. § 371 toInternational Patent Application No. PCT/JP2018/007900, filed Mar. 1,2018, which claims priority to and the benefit of Japanese PatentApplication No. 2017-038844, filed on Mar. 1, 2017. The contents ofthese applications are hereby incorporated by reference in theirentireties.

TECHNICAL FIELD

The present invention relates to a polycarbonate-polyorganosiloxanecopolymer, a polycarbonate-based resin composition including thecopolymer, and a molded article of the composition.

BACKGROUND ART

A polycarbonate-polyorganosiloxane copolymer (hereinafter sometimesabbreviated as “PC-POS copolymer”) has been attracting attention becauseof its excellent properties, such as high impact resistance, chemicalresistance, and flame retardancy. Accordingly, thepolycarbonate-polyorganosiloxane copolymer has been expected to bewidely utilized in various fields, such as the field of electrical andelectronic equipment and the field of automobiles. In particular, theutilization of the polycarbonate-polyorganosiloxane copolymer in casingsfor a cellular phone, a mobile personal computer, a digital camera, avideo camera, an electric tool, a communication base station, a battery,and the like, and in other commodities has been expanding.

In normal cases, a homopolycarbonate using2,2-bis(4-hydroxyphenyl)propane [common name: bisphenol A] as a dihydricphenol serving as a raw material has been generally used as a typicalpolycarbonate. A polycarbonate-polyorganosiloxane copolymer using apolyorganosiloxane as a copolymerizable monomer has been known forimproving the physical properties of the homopolycarbonate, such asflame retardancy and impact resistance (Patent Document 1).

Examples of an approach to further improving the impact resistance of apolycarbonate resin containing the polycarbonate-polyorganosiloxanecopolymer may include an approach involving using a polyorganosiloxanehaving a long chain length, and an approach involving increasing theamount of the polyorganosiloxane in the polycarbonate-polyorganosiloxanecopolymer as described in Patent Documents 2 and 3.

CITATION LIST Patent Document

Patent Document 1: JP 2662310 B2

Patent Document 2: JP 2011-21127 A

Patent Document 3: JP 2012-246390 A

SUMMARY OF INVENTION Technical Problem

As described above, the polycarbonate-polyorganosiloxane copolymer isexcellent in impact resistance, but it has been required to obtain apolycarbonate-based resin composition further improved in chemicalresistance.

Solution to Problem

The inventors of the present invention have found that, when apolycarbonate-polyorganosiloxane copolymer whose polyorganosiloxaneblock concentration in a specific molecular weight region is equal to ormore than a certain value is used, a polycarbonate-polyorganosiloxanecopolymer having more excellent impact resistance is obtained withoutthe extension of the chain length of a polyorganosiloxane block or anincrease in content thereof. In addition, the inventors have found thatthe addition of a polyester-based resin to a polycarbonate-based resinincluding the polycarbonate-polyorganosiloxane copolymer provides apolycarbonate-based resin composition further excellent in chemicalresistance.

That is, the present invention relates to the following items [1] to[27].

[1] A polycarbonate-polyorganosiloxane copolymer, comprising:

polycarbonate blocks (A-1) each formed of a repeating unit representedby the following general formula (I); and

polyorganosiloxane blocks (A-2) each containing a repeating unitrepresented by the following general formula (II),

wherein the polycarbonate-polyorganosiloxane copolymer satisfies thefollowing expression (F1a):15≤wM1  (F1a)wherein wM1 represents an average content (mass %) of thepolyorganosiloxane blocks (A-2) in polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using apolycarbonate as a conversion reference of from 56,000 or more to200,000 or less among polycarbonate-polyorganosiloxane copolymersobtained through separation of the polycarbonate-polyorganosiloxanecopolymer by gel permeation chromatography;

wherein R¹ and R² each independently represent a halogen atom, an alkylgroup having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6carbon atoms, X represents a single bond, an alkylene group having 1 to8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, acycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene grouphaving 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene grouphaving 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15carbon atoms, —S—, —SO—, —SO₂—, —O—, or —CO—, R³ and R⁴ eachindependently represent a hydrogen atom, a halogen atom, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,or an aryl group having 6 to 12 carbon atoms, and “a” and “b” eachindependently represent an integer of from 0 to 4.

[2] The polycarbonate-polyorganosiloxane copolymer according to theabove-mentioned item [1], wherein the polycarbonate-polyorganosiloxanecopolymer satisfies the following expression (F1a′):13≤wM2  (F1a′)wherein wM2 represents an average content (mass %) of thepolyorganosiloxane blocks (A-2) in polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using thepolycarbonate as a conversion reference of from 16,000 or more to lessthan 56,000 among the polycarbonate-polyorganosiloxane copolymersobtained through the separation of the polycarbonate-polyorganosiloxanecopolymer by the gel permeation chromatography.

[3] The polycarbonate-polyorganosiloxane copolymer according to theabove-mentioned item [1] or [2], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F1b):100<wM1/wA×100  (F1b)wherein wM1 is as described above, and wA represents an average content(mass %) of the polyorganosiloxane blocks (A-2) in thepolycarbonate-polyorganosiloxane copolymer.

[4] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [3], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F2):wM2<wM1  (F2)wherein wM1 and wM2 are as described above.

[5] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [4], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F3):wM3<wM2  (F3)wherein wM2 is as described above, and wM3 represents an average content(mass %) of the polyorganosiloxane blocks (A-2) inpolycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 4,500 or more to less than 16,000 among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography.

[6] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [5], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F4a):50≤nM1  (F4a)wherein nM1 represents an average chain length of the polyorganosiloxaneblocks (A-2) in the polycarbonate-polyorganosiloxane copolymers eachhaving a molecular weight determined by using the polycarbonate as aconversion reference of from 56,000 or more to 200,000 or less among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography.

[7] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [6], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F4b):100<nM1/nA×100  (F4b)wherein nM1 is as described above, and nA represents an average chainlength of the polyorganosiloxane blocks (A-2) in thepolycarbonate-polyorganosiloxane copolymer.

[8] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [7], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F5):nM2<nM1  (F5)wherein nM1 is as described above, and nM2 represents an average chainlength of the polyorganosiloxane blocks (A-2) inpolycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 16,000 or more to less than 56,000 among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography.

[9] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [8], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F6):nM3<nM2  (F6)wherein nM2 is as described above, and nM3 represents an average chainlength of the polyorganosiloxane blocks (A-2) inpolycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 4,500 or more to less than 16,000 among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography.

[10] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [9], wherein thepolycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 56,000 or more to 200,000 or less among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography satisfy the following expression (F7a):1.5≤iPOS/iPC  (F7a)wherein iPOS represents an average content (mol) of linking groups ofthe polycarbonate blocks (A-1) and the polyorganosiloxane blocks (A-2),and iPC represents an average content (mol) of terminal groups of thepolycarbonate blocks (A-1).

[11] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [10], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F7b):100<iM1/iA×100  (F7b)wherein iM1 represents a ratio (iPOS/iPC) of iPOS to iPC in thepolycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 56,000 or more to 200,000 or less among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography, and iA represents a ratio (iPOS/iPC) of iPOSto iPC in the polycarbonate-polyorganosiloxane copolymer.

[12] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [11], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F8):iM2<iM1  (F8)wherein iM1 is as described above, and iM2 represents a ratio (iPOS/iPC)of iPOS to iPC in polycarbonate-polyorganosiloxane copolymers eachhaving a molecular weight determined by using the polycarbonate as aconversion reference of from 16,000 or more to less than 56,000 amongthe polycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography.

[13] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [12], wherein thepolycarbonate-polyorganosiloxane copolymer satisfies the followingexpression (F9):iM3<iM2  (F9)wherein iM2 is as described above, and iM3 represents a ratio (iPOS/iPC)of iPOS to iPC in polycarbonate-polyorganosiloxane copolymers eachhaving a molecular weight determined by using the polycarbonate as aconversion reference of from 4,500 or more to less than 16,000 among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography.

[14] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [13], wherein the aromaticpolycarbonate-based resin (B) contains a polycarbonate block including,in a main chain thereof, a repeating unit represented by the followinggeneral formula (III):

wherein R³⁰ and R³¹ each independently represent a halogen atom, analkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6carbon atoms, X′ represents a single bond, an alkylene group having 1 to8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, acycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene grouphaving 5 to 15 carbon atoms, —S—, —SO—, —SO₂—, —O—, or —CO—, and “d” and“e” each independently represent an integer of from 0 to 4.

[15] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [14], wherein the polyorganosiloxaneblocks (A-2) have an average chain length of from 30 or more to 500 orless.

[16] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [15], wherein the polyorganosiloxaneblocks (A-2) have an average chain length of from 55 or more to 500 orless.

[17] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [16], wherein the polyorganosiloxaneblocks (A-2) have an average chain length of from 55 or more to 85 orless.

[18] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [17], wherein a content of thepolyorganosiloxane blocks (A-2) in the polycarbonate-polyorganosiloxanecopolymer (A) is from 5 mass % or more to 70 mass % or less.

[19] The polycarbonate-polyorganosiloxane copolymer according to any oneof the above-mentioned items [1] to [18], wherein thepolycarbonate-polyorganosiloxane copolymer (A) has a viscosity-averagemolecular weight (Mv) of from 9,000 or more to 50,000 or less.

[20] A polycarbonate-based resin composition, comprising:

the polycarbonate-polyorganosiloxane copolymer (A) of any one of theabove-mentioned items [1] to [19];

an aromatic polycarbonate-based resin (B) except thepolycarbonate-polyorganosiloxane copolymer (A); and

a polyester-based resin (C),

wherein the polyester-based resin (C) is blended with respect to 100parts by mass of a total of the polycarbonate-polyorganosiloxanecopolymer (A) and the aromatic polycarbonate-based resin (B), and

wherein a ratio of the polycarbonate-polyorganosiloxane copolymer (A)and the aromatic polycarbonate-based resin (B) in 100 mass % of a totalamount of the polycarbonate-polyorganosiloxane copolymer (A) and thearomatic polycarbonate-based resin (B), and the polyester-based resin(C) is from 50 mass % or more to 99 mass % or less.

[21] The polycarbonate-based resin composition according to theabove-mentioned item [20], wherein a mass ratio “(A)/(B)” of thepolycarbonate-polyorganosiloxane copolymer (A) to the aromaticpolycarbonate-based resin (B) is from 0.1/99.9 to 99.9/0.1.

[22] The polycarbonate-based resin composition according to theabove-mentioned item [20] or [21], wherein a content of thepolyorganosiloxane blocks (A-2) with respect to a total of thepolycarbonate-polyorganosiloxane copolymer (A) and the aromaticpolycarbonate-based resin (B) is from 0.1 mass % or more to 10 mass % orless.

[23] The polycarbonate-based resin composition according to any one ofthe above-mentioned items [20] to [22], wherein a polycarbonate-basedresin formed of the polycarbonate-polyorganosiloxane copolymer (A) andthe aromatic polycarbonate-based resin (B) has a viscosity-averagemolecular weight (Mv) of from 9,000 or more to 50,000 or less.

[24] The polycarbonate-based resin composition according to any one ofthe above-mentioned items [20] to [23], wherein the polyester-basedresin (C) comprises at least one selected from a polyethyleneterephthalate and a polybutylene terephthalate.

[25] A molded article, which is obtained by molding thepolycarbonate-based resin composition of any one of the above-mentioneditems [20] to [24].

[26] The molded article according to the above-mentioned item [25],wherein the molded article comprises a casing for electrical andelectronic equipment.

[27] The molded article according to the above-mentioned item [25],wherein the molded article comprises a part for an automobile and abuilding material.

Advantageous Effects of Invention

According to the present invention, the polycarbonate-polyorganosiloxanecopolymer having more excellent impact resistance, thepolycarbonate-based resin composition including the polycarbonate-basedresins including the polycarbonate-polyorganosiloxane copolymer and thepolyester-based resin, the composition being excellent in chemicalresistance, and the molded article of the composition can be obtained.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a graph in which a polycarbonate-polyorganosiloxane copolymeris fractionated into 5 fractions for respective retention times by gelpermeation chromatography.

FIG. 2 is a graph showing a polyorganosiloxane block content for eachmolecular weight determined by the gel permeation chromatography throughthe use of a polycarbonate as a conversion reference in ProductionExample 1.

FIG. 3 is a view for illustrating an example of a linking group of apolyorganosiloxane block and a polycarbonate block, and an example of aterminal group of the polycarbonate block.

DESCRIPTION OF EMBODIMENTS

The inventors of the present invention have made extensiveinvestigations, and as a result, have found that, when apolycarbonate-polyorganosiloxane copolymer whose polyorganosiloxaneblock concentration in a specific molecular weight region is equal to ormore than a certain value is used, a polycarbonate-polyorganosiloxanecopolymer having more excellent impact resistance is obtained withoutthe extension of the chain length of a polyorganosiloxane block or anincrease in content thereof. In addition, the inventors have found thatthe addition of a polyester-based resin to a polycarbonate-based resinincluding the polycarbonate-polyorganosiloxane copolymer provides apolycarbonate-based resin composition having excellent chemicalresistance, and a molded article of the composition. Detaileddescription is given below.

The term “XX to YY” as used herein means “from XX or more to YY orless.” In this description, a specification considered to be preferredmay be arbitrarily adopted, and a combination of preferredspecifications is more preferred.

<Polycarbonate-Polyorganosiloxane Copolymer>

A polycarbonate-polyorganosiloxane copolymer according to a firstembodiment of the present invention comprises: polycarbonate blocks(A-1) each formed of a repeating unit represented by the followinggeneral formula (I); and polyorganosiloxane blocks (A-2) each containinga repeating unit represented by the following general formula (II),wherein the polycarbonate-polyorganosiloxane copolymer satisfies thefollowing expression (F1a):15≤wM1  (F1a)wherein wM1 represents an average content (mass %) of thepolyorganosiloxane blocks (A-2) in polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using apolycarbonate as a conversion reference of from 56,000 or more to200,000 or less among polycarbonate-polyorganosiloxane copolymersobtained through separation of the polycarbonate-polyorganosiloxanecopolymer by gel permeation chromatography;

wherein R¹ and R² each independently represent a halogen atom, an alkylgroup having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6carbon atoms, X represents a single bond, an alkylene group having 1 to8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, acycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene grouphaving 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene grouphaving 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15carbon atoms, —S—, —SO—, —SO₂—, —O—, or —CO—, R³ and R⁴ eachindependently represent a hydrogen atom, a halogen atom, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,or an aryl group having 6 to 12 carbon atoms, and “a” and “b” eachindependently represent an integer of from 0 to 4.

In the general formula (I), examples of the halogen atom that R¹ and R²each independently represent include a fluorine atom, a chlorine atom, abromine atom, and an iodine atom.

Examples of the alkyl group that R¹ and R² each independently representinclude a methyl group, an ethyl group, a n-propyl group, an isopropylgroup, various butyl groups (the term “various” means that a lineargroup and all kinds of branched groups are included, and in thisdescription, the same holds true for the following), various pentylgroups, and various hexyl groups. Examples of the alkoxy group that R¹and R² each independently represent include alkoxy groups having theabove-mentioned alkyl groups as alkyl group moieties.

Examples of the alkylene group represented by X include a methylenegroup, an ethylene group, a trimethylene group, a tetramethylene group,and a hexamethylene group. Among them, an alkylene group having 1 to 5carbon atoms is preferred. Examples of the alkylidene group representedby X include an ethylidene group and an isopropylidene group. Examplesof the cycloalkylene group represented by X include a cyclopentanediylgroup, a cyclohexanediyl group, and a cyclooctanediyl group. Among them,a cycloalkylene group having 5 to 10 carbon atoms is preferred. Examplesof the cycloalkylidene group represented by X include a cyclohexylidenegroup, a 3,5,5-trimethylcyclohexylidene group, and a 2-adamantylidenegroup. Among them, a cycloalkylidene group having 5 to 10 carbon atomsis preferred, and a cycloalkylidene group having 5 to 8 carbon atoms ismore preferred. Examples of the aryl moiety of the arylalkylene grouprepresented by X include aryl groups each having 6 to 14 ring-formingcarbon atoms, such as a phenyl group, a naphthyl group, a biphenylgroup, and an anthryl group, and examples of the alkylene group includethe above-mentioned alkylene groups. Examples of the aryl moiety of thearylalkylidene group represented by X include aryl groups each having 6to 14 ring-forming carbon atoms, such as a phenyl group, a naphthylgroup, a biphenyl group, and an anthryl group, and examples of thealkylidene group may include the above-mentioned alkylidene groups.

“a” and “b” each independently represent an integer of from 0 to 4,preferably from 0 to 2, more preferably 0 or 1.

Among them, a repeating unit in which “a” and “b” each represent 0, andX represents a single bond or an alkylene group having 1 to 8 carbonatoms, or a repeating unit in which “a” and “b” each represent 0, and Xrepresents an alkylene group having 3 carbon atoms, in particular anisopropylidene group is suitable.

In the general formula (II), examples of the halogen atom represented byR³ or R⁴ include a fluorine atom, a chlorine atom, a bromine atom, andan iodine atom. Examples of the alkyl group represented by R³ or R⁴include a methyl group, an ethyl group, a n-propyl group, an isopropylgroup, various butyl groups, various pentyl groups, and various hexylgroups. Examples of the alkoxy group represented by R³ or R⁴ includealkoxy groups having the above-mentioned alkyl groups as alkyl groupmoieties. Examples of the aryl group represented by R³ or R⁴ include aphenyl group and a naphthyl group.

R³ and R⁴ each preferably represent a hydrogen atom, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,or an aryl group having 6 to 12 carbon atoms, and each more preferablyrepresent a methyl group.

More specifically, the polyorganosiloxane block (A-2) containing therepeating unit represented by the general formula (II) preferably has aunit represented by any one of the following general formulae (II-I) to(II-III):

wherein R³ to R⁶ each independently represent a hydrogen atom, a halogenatom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and aplurality of R³, R⁴, R⁵, or R⁶ may be identical to or different fromeach other, Y represents —R⁷O—, —R⁷COO—, —R⁷NH—, —R⁷NR⁸—, —COO—, —S—,—R⁷COO—R⁹—O—, or —R⁷O—R¹⁰—O—, and a plurality of Ys may be identical toor different from each other, the R⁷ represents a single bond, a linear,branched, or cyclic alkylene group, an aryl-substituted alkylene group,a substituted or unsubstituted arylene group, or a diarylene group, R⁸represents an alkyl group, an alkenyl group, an aryl group, or anaralkyl group, R⁹ represents a diarylene group, R¹⁰ represents a linear,branched, or cyclic alkylene group, or a diarylene group, β represents adivalent group derived from a diisocyanate compound, or a divalent groupderived from a dicarboxylic acid or a halide of a dicarboxylic acid, “n”represents the chain length of the polyorganosiloxane, and n−1, and “p”and “q” each represent the number of repetitions of a polyorganosiloxaneunit and each represent an integer of 1 or more, and the sum of “p” and“q” is n−2.

Examples of the halogen atom that R³ to R⁶ each independently representinclude a fluorine atom, a chlorine atom, a bromine atom, and an iodineatom. Examples of the alkyl group that R³ to R⁶ each independentlyrepresent include a methyl group, an ethyl group, a n-propyl group, anisopropyl group, various butyl groups, various pentyl groups, andvarious hexyl groups. Examples of the alkoxy group that R³ to R⁶ eachindependently represent include alkoxy groups having the above-mentionedalkyl groups as alkyl group moieties. Examples of the aryl group that R³to R⁶ each independently represent include a phenyl group and a naphthylgroup.

R³ to R⁶ each preferably represent a hydrogen atom, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,or an aryl group having 6 to 12 carbon atoms.

R³ to R⁶ in the general formula (II-I), the general formula (II-II),and/or the general formula (II-III) each preferably represent a methylgroup.

The linear or branched alkylene group represented by R⁷ in —R⁷O—,—R⁷COO—, —R⁷NH—, —R⁷NR⁸—, —R⁷COO—R⁹—O—, or —R⁷O—R¹⁰—O— represented by Yis, for example, an alkylene group having 1 to 8 carbon atoms,preferably 1 to 5 carbon atoms, and the cyclic alkylene grouprepresented by R⁷ is, for example, a cycloalkylene group having 5 to 15carbon atoms, preferably 5 to 10 carbon atoms.

The aryl-substituted alkylene group represented by R⁷ may have asubstituent, such as an alkoxy group or an alkyl group, on its aromaticring, and a specific structure thereof may be, for example, a structurerepresented by the following general formula (i) or (ii). When the blockhas the aryl-substituted alkylene group, the alkylene group is bonded toSi.

wherein “c” represents a positive integer and typically represents aninteger of from 1 to 6.

The diarylene group represented by any one of R⁷, R⁹, and R¹⁰ refers toa group in which two arylene groups are linked to each other directly orthrough a divalent organic group, and is specifically a group having astructure represented by —Ar¹—W—Ar²—. Here, Ar¹ and Ar² each representan arylene group, and W represents a single bond or a divalent organicgroup. Examples of the divalent organic group represented by W includean isopropylidene group, a methylene group, a dimethylene group, and atrimethylene group.

Examples of the arylene group represented by any one of R⁷, Ar¹, and Ar²include arylene groups each having 6 to 14 ring-forming carbon atoms,such as a phenylene group, a naphthylene group, a biphenylene group, andan anthrylene group. Those arylene groups may each have an arbitrarysubstituent, such as an alkoxy group or an alkyl group.

The alkyl group represented by R⁸ is a linear or branched group having 1to 8, preferably 1 to 5 carbon atoms. The alkenyl group represented byR⁸ is, for example, a linear or branched group having 2 to 8, preferably2 to 5 carbon atoms. The aryl group represented by R⁸ is, for example, aphenyl group or a naphthyl group. The aralkyl group represented by R⁸is, for example, a phenylmethyl group or a phenylethyl group.

The linear, branched, or cyclic alkylene group represented by R¹⁰ is thesame as that represented by R⁷.

Y preferably represents —R⁷O—. R⁷ preferably represents anaryl-substituted alkylene group, in particular a residue of aphenol-based compound having an alkyl group, and more preferablyrepresents an organic residue derived from allylphenol or an organicresidue derived from eugenol.

With regard to “p” and “q” in the formula (II-II), it is preferred thatp=q.

In addition, β represents a divalent group derived from a diisocyanatecompound, or a divalent group derived from a dicarboxylic acid or ahalide of a dicarboxylic acid, and examples thereof include divalentgroups represented by the following general formulae (iii) to (vii).

The average chain length “n” of the polyorganosiloxane blocks (A-2) inthe PC-POS copolymer (A) is preferably 30 or more, more preferably 35 ormore, still more preferably 40 or more, still further more preferably 50or more, particularly preferably 55 or more, most preferably 60 or more.In addition, the average chain length is preferably 500 or less, morepreferably 400 or less, still more preferably 300 or less, still furthermore preferably 200 or less, particularly preferably 120 or less, mostpreferably 85 or less. The average chain length is calculated by nuclearmagnetic resonance (NMR) measurement. When the average chain length “n”falls within the range of from 30 or more to 500 or less, more excellentimpact resistance can be obtained. In addition, the average chain length“n” of the polyorganosiloxane blocks (A-2) preferably falls within therange of from 55 or more to 500 or less from the viewpoint that moreexcellent impact resistance is obtained.

The content of the polyorganosiloxane blocks (A-2) in the PC-POScopolymer (A) is preferably 5 mass % or more, more preferably 6 mass %or more, still more preferably 10 mass % or more, still further morepreferably 14 mass % or more, still further more preferably 18 mass % ormore, particularly preferably 21 mass % or more, and is preferably 70mass % or less, more preferably 50 mass % or less, still more preferably45 mass % or less, particularly preferably 40 mass % or less. When thecontent of the polyorganosiloxane blocks in the PC-POS copolymer (A)falls within the range, more excellent impact resistance can beobtained.

The viscosity-average molecular weight (Mv) of the PC-POS copolymer (A)may be appropriately adjusted by using, for example, a molecular weightmodifier (terminal stopper) so as to be a target molecular weight inaccordance with applications or products in which the copolymer is used.However, the viscosity-average molecular weight is preferably 9,000 ormore, more preferably 12,000 or more, still more preferably 14,000 ormore, particularly preferably 16,000 or more, and is preferably 50,000or less, more preferably 30,000 or less, still more preferably 23,000 orless, particularly preferably 22,000 or less, most preferably 20,000 orless. When the viscosity-average molecular weight is 9,000 or more, asufficient strength of a molded article can be obtained. When theviscosity-average molecular weight is 50,000 or less, injection moldingor extrusion molding can be performed at the temperature at which theheat deterioration of the copolymer does not occur.

The viscosity-average molecular weight (Mv) is a value calculated fromthe following Schnell's equation by measuring the limiting viscosity [η]of a methylene chloride solution at 20° C.[η]=1.23×10⁻⁵ ×Mv ^(0.83)

The polycarbonate-polyorganosiloxane copolymer (A) may be produced by aknown production method, such as an interfacial polymerization method(phosgene method), a pyridine method, or an ester exchange method.Particularly in the case of the interfacial polymerization method, astep of separating an organic phase containing the PC-POS copolymer (A)and an aqueous phase containing an unreacted product, a catalystresidue, or the like becomes easier, and hence the separation of theorganic phase containing the PC-POS copolymer (A) and the aqueous phasein each washing step based on alkali washing, acid washing, or purewater washing becomes easier. Accordingly, the PC-POS copolymer (A) isefficiently obtained. With regard to a method of producing the PC-POScopolymer (A), reference may be made to, for example, a method describedin JP 2010-241943 A.

Specifically, the PC-POS copolymer (A) may be produced by: dissolving apolycarbonate oligomer produced in advance to be described later and apolyorganosiloxane in a water-insoluble organic solvent (e.g., methylenechloride); adding a solution of a dihydric phenol-based compound (e.g.,bisphenol A) in an aqueous alkali compound (e.g., aqueous sodiumhydroxide) to the solution; and subjecting the mixture to an interfacialpolycondensation reaction through the use of a tertiary amine (e.g.,triethylamine) or a quaternary ammonium salt (e.g.,trimethylbenzylammonium chloride) as a polymerization catalyst in thepresence of a terminal stopper (a monohydric phenol, such asp-tert-butylphenol). In addition, the PC-POS copolymer (A) may also beproduced by copolymerizing the polyorganosiloxane and a dihydric phenol,and phosgene, a carbonate ester, or a chloroformate.

When the polycarbonate-polyorganosiloxane copolymer (A) in thepolycarbonate-based resin composition of the present application isproduced by, for example, causing the polycarbonate oligomer and apolyorganosiloxane raw material to react with each other in an organicsolvent, and then causing the resultant to react with the dihydricphenol, the solid content weight (g/L) of the polycarbonate oligomer in1 L of a mixed solution of the organic solvent and the polycarbonateoligomer preferably falls within the range of from 80 g/L or more to 200g/L or less. The solid content weight is more preferably 90 g/L or more,still more preferably 100 g/L or more, and is more preferably 180 g/L orless, still more preferably 170 g/L or less.

A polyorganosiloxane represented by the following general formula (1),general formula (2), and/or general formula (3) may be used as thepolyorganosiloxane serving as a raw material:

wherein

R³ to R⁶, Y, β, n−1, “p”, and “q” are as described above, and specificexamples and preferred examples thereof are also the same as thosedescribed above, and

Z represents a hydrogen atom or a halogen atom, and a plurality of Z maybe identical to or different from each other.

Examples of the polyorganosiloxane represented by the general formula(1) include compounds each represented by any one of the followinggeneral formulae (1-1) to (1-11):

wherein in the general formulae (1-1) to (1-11), R³ to R⁶, “n”, and R⁸are as defined above, and preferred examples thereof are also the sameas those described above, and “c” represents a positive integer andtypically represents an integer of from 1 to 6.

Among them, a phenol-modified polyorganosiloxane represented by thegeneral formula (1-1) is preferred from the viewpoint of its ease ofpolymerization. In addition, anα,ω-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane, which is onecompound represented by the general formula (1-2), or anα,ω-bis[3-(4-hydroxy-3-methoxyphenyl)propyl]polydimethylsiloxane, whichis one compound represented by the general formula (1-3), is preferredfrom the viewpoint of its ease of availability.

In addition to the foregoing, a compound having a structure representedby the following general formula (4) may be used as a polyorganosiloxaneraw material:

wherein R³ and R⁴ are identical to those described above. The averagechain length of the polyorganosiloxane block represented by the generalformula (4) is (r×m), and the range of the (r×m) is the same as that ofthe “n”.

When the compound represented by the general formula (4) is used as apolyorganosiloxane raw material, the polyorganosiloxane block (A-2)preferably has a unit represented by the following general formula(II-IV):

wherein R³, R⁴, “r”, and “m” are as described above.

The copolymer may include a structure represented by the followinggeneral formula (II-V) as the polyorganosiloxane block (A-2):

wherein R¹⁸ to R²¹ each independently represent a hydrogen atom or analkyl group having 1 to 13 carbon atoms, R²² represents an alkyl grouphaving 1 to 6 carbon atoms, a hydrogen atom, a halogen atom, a hydroxygroup, an alkoxy group having 1 to 6 carbon atoms, or an aryl grouphaving 6 to 14 carbon atoms, Q² represents a divalent aliphatic grouphaving 1 to 10 carbon atoms, and “n” represents an average chain lengthand represents from 30 to 70.

In the general formula (II-V), examples of the alkyl group having 1 to13 carbon atoms that R¹⁸ to R²¹ each independently represent include amethyl group, an ethyl group, a n-propyl group, an isopropyl group,various butyl groups, various pentyl groups, various hexyl groups,various heptyl groups, various octyl groups, a 2-ethylhexyl group,various nonyl groups, various decyl groups, various undecyl groups,various dodecyl groups, and various tridecyl groups. Among them, R¹⁸ toR²¹ each preferably represent a hydrogen atom or an alkyl group having 1to 6 carbon atoms, and it is more preferred that all of R¹⁸ to R²¹ eachrepresent a methyl group.

Examples of the alkyl group having 1 to 6 carbon atoms represented byR²² include a methyl group, an ethyl group, a n-propyl group, anisopropyl group, various butyl groups, various pentyl groups, andvarious hexyl groups. Examples of the halogen atom represented by R²²include a fluorine atom, a chlorine atom, a bromine atom, and an iodineatom. An example of the alkoxy group having 1 to 6 carbon atomsrepresented by R²² is an alkoxy group whose alkyl group moiety is thealkyl group described above. In addition, examples of the aryl grouphaving 6 to 14 carbon atoms represented by R²² include a phenyl group, atoluyl group, a dimethylphenyl group, and a naphthyl group.

Among them, R²² preferably represents a hydrogen atom or an alkoxy grouphaving 1 to 6 carbon atoms, more preferably represents a hydrogen atomor an alkoxy group having 1 to 3 carbon atoms, and still more preferablyrepresents a hydrogen atom.

The divalent aliphatic group having 1 to 10 carbon atoms represented byQ² is preferably a linear or branched divalent saturated aliphatic grouphaving 1 to 10 carbon atoms. The number of carbon atoms of the saturatedaliphatic group is preferably from 1 to 8, more preferably from 2 to 6,still more preferably from 3 to 6, still further more preferably from 4to 6. In addition, the average chain length “n” is as described above.

A preferred mode of the constituent unit (II-V) may be, for example, astructure represented by the following general formula (II-VI):

wherein “n” is identical to that described above.

The polyorganosiloxane block (A-2) represented by the general formula(II-V) or (II-VI) may be obtained by using a polyorganosiloxane rawmaterial represented by the following general formula (5) or (6):

wherein R¹⁸ to R²², Q², and “n” are as described above;

wherein “n” is as described above.

A method of producing the polyorganosiloxane is not particularlylimited. According to, for example, a method described in JP 11-217390A, a crude polyorganosiloxane may be obtained by: causingcyclotrisiloxane and disiloxane to react with each other in the presenceof an acid catalyst to synthesize α,ω-dihydrogen organopentasiloxane;and then subjecting the α,ω-dihydrogen organopentasiloxane to anaddition reaction with, for example, a phenolic compound (e.g.,2-allylphenol, 4-allylphenol, eugenol, or 2-propenylphenol) in thepresence of a catalyst for a hydrosilylation reaction. In addition,according to a method described in JP 2662310 B2, the crudepolyorganosiloxane may be obtained by: causingoctamethylcyclotetrasiloxane and tetramethyldisiloxane to react witheach other in the presence of sulfuric acid (acid catalyst); andsubjecting the resultant α,ω-dihydrogen organopolysiloxane to anaddition reaction with the phenolic compound or the like in the presenceof the catalyst for a hydrosilylation reaction in the same manner asthat described above. The α,ω-dihydrogen organopolysiloxane may be usedafter its chain length “n” has been appropriately adjusted in accordancewith its polymerization conditions, or a commercial α,ω-dihydrogenorganopolysiloxane may be used.

Examples of the catalyst for a hydrosilylation reaction includetransition metal-based catalysts. Among them, a platinum-based catalystis preferably used in terms of a reaction rate and selectivity. Specificexamples of the platinum-based catalyst include chloroplatinic acid, analcohol solution of chloroplatinic acid, an olefin complex of platinum,a complex of platinum and a vinyl group-containing siloxane,platinum-supported silica, and platinum-supported activated carbon.

The crude polyorganosiloxane is preferably brought into contact with anadsorbent to cause the adsorbent to adsorb and remove a transition metalderived from a transition metal-based catalyst in the crudepolyorganosiloxane, the catalyst having been used as the catalyst for ahydrosilylation reaction.

An adsorbent having an average pore diameter of, for example, 1,000 Å orless may be used as the adsorbent. When the average pore diameter is1,000 Å or less, the transition metal in the crude polyorganosiloxanecan be efficiently removed. From such viewpoint, the average porediameter of the adsorbent is preferably 500 Å or less, more preferably200 Å or less, still more preferably 150 Å or less, still further morepreferably 100 Å or less. In addition, from the same viewpoint, theadsorbent is preferably a porous adsorbent.

Although the adsorbent is not particularly limited as long as theadsorbent has the above-mentioned average pore diameter, for example,activated clay, acid clay, activated carbon, synthetic zeolite, naturalzeolite, activated alumina, silica, a silica-magnesia-based adsorbent,diatomaceous earth, or cellulose may be used, and at least one selectedfrom the group consisting of activated clay, acid clay, activatedcarbon, synthetic zeolite, natural zeolite, activated alumina, silica,and a silica-magnesia-based adsorbent is preferred.

After the adsorbent has been caused to adsorb the transition metal inthe crude polyorganosiloxane, the adsorbent may be separated from thepolyorganosiloxane by arbitrary separating means. Examples of the meansfor separating the adsorbent from the polyorganosiloxane include afilter and centrifugal separation. When the filter is used, a filtersuch as a membrane filter, a sintered metal filter, or a glass fiberfilter may be used. Among them, a membrane filter is particularlypreferably used.

The average particle diameter of the adsorbent is typically from 1 μm ormore to 4 mm or less, preferably from 1 μm or more to 100 μm or lessfrom the viewpoint that the adsorbent is separated from thepolyorganosiloxane after the adsorption of the transition metal.

When the adsorbent is used, its usage amount is not particularlylimited. The porous adsorbent may be used in an amount in the range offrom preferably 1 part by mass or more, more preferably 2 parts by massor more to preferably 30 parts by mass or less, more preferably 20 partsby mass or less with respect to 100 parts by mass of the crudepolyorganosiloxane.

When the crude polyorganosiloxane to be treated has so high a molecularweight that the polyorganosiloxane is not in a liquid state, thepolyorganosiloxane may be heated to such a temperature as to be in aliquid state at the time of the performance of the adsorption with theadsorbent and the separation of the adsorbent. Alternatively, theadsorption and the separation may be performed after thepolyorganosiloxane has been dissolved in a solvent, such as methylenechloride or hexane.

A polyorganosiloxane having a desired molecular weight distribution isobtained by regulating its molecular weight distribution through, forexample, the blending of a plurality of polyorganosiloxanes. With regardto the blending, a crude polyorganosiloxane having a desired molecularweight distribution may be obtained by blending a plurality ofα,ω-dihydrogen organopolysiloxanes and then subjecting a phenoliccompound or the like to an addition reaction with the resultant in thepresence of a catalyst for a hydrosilylation reaction. Purification,such as the removal of the catalyst for a hydrosilylation reaction, maybe performed after a plurality of crude polyorganosiloxanes have beenblended. A plurality of polyorganosiloxanes after the purification maybe blended. In addition, a molecular weight distribution may beappropriately adjusted depending on a polymerization condition at thetime of the production of a polyorganosiloxane. Further, a desiredmolecular weight distribution may be obtained by fractionating only partof existing polyorganosiloxanes through means such as various kinds ofseparation.

The polycarbonate oligomer may be produced by a reaction between adihydric phenol and a carbonate precursor, such as phosgene ortriphosgene, in an organic solvent, such as methylene chloride,chlorobenzene, or chloroform. When the polycarbonate oligomer isproduced by using an ester exchange method, the oligomer may be producedby a reaction between the dihydric phenol and a carbonate precursor,such as diphenyl carbonate.

A dihydric phenol represented by the following general formula (viii) ispreferably used as the dihydric phenol:

wherein R¹, R², “a”, “b”, and X are as described above.

Examples of the dihydric phenol represented by the general formula(viii) include: bis(hydroxyphenyl)alkane-based dihydric phenols, such as2,2-bis(4-hydroxyphenyl)propane [bisphenol A],bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl) ethane, and2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane; 4,4′-dihydroxydiphenyl;bis(4-hydroxyphenyl)cycloalkanes; bis(4-hydroxyphenyl) oxide;bis(4-hydroxyphenyl) sulfide; bis(4-hydroxyphenyl) sulfone;bis(4-hydroxyphenyl) sulfoxide; and bis(4-hydroxyphenyl) ketone. Thosedihydric phenols may be used alone or as a mixture thereof.

Among them, bis(hydroxyphenyl)alkane-based dihydric phenols arepreferred, and bisphenol A is more preferred. When bisphenol A is usedas the dihydric phenol, the PC-POS copolymer is such that in the generalformula (i), X represents an isopropylidene group and a=b=0.

Examples of the dihydric phenol except bisphenol A includebis(hydroxyaryl)alkanes, bis(hydroxyaryl)cycloalkanes, dihydroxyarylethers, dihydroxydiaryl sulfides, dihydroxydiaryl sulfoxides,dihydroxydiaryl sulfones, dihydroxydiphenyls, dihydroxydiaryl fluorenes,and dihydroxydiaryl adamantanes. Those dihydric phenols may be usedalone or as a mixture thereof.

Examples of the bis(hydroxyaryl)alkanes includebis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane,2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane,bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane,2,2-bis(4-hydroxy-3-methylphenyl)propane,bis(4-hydroxyphenyl)naphthylmethane,1,1-bis(4-hydroxy-3-tert-butylphenyl)propane,2,2-bis(4-hydroxy-3-bromophenyl)propane,2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane,2,2-bis(4-hydroxy-3-chlorophenyl)propane,2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, and2,2-bis(4-hydroxy-3,5-dibromophenyl)propane.

Examples of the bis(hydroxyaryl)cycloalkanes include1,1-bis(4-hydroxyphenyl)cyclopentane,1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)-3,5,5-trimethylcyclohexane,2,2-bis(4-hydroxyphenyl)norbornane, and1,1-bis(4-hydroxyphenyl)cyclododecane. Examples of the dihydroxyarylethers include 4,4′-dihydroxydiphenyl ether and4,4′-dihydroxy-3,3′-dimethylphenyl ether.

Examples of the dihydroxydiaryl sulfides include 4,4′-dihydroxydiphenylsulfide and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfide. Examples ofthe dihydroxydiaryl sulfoxides include 4,4′-dihydroxydiphenyl sulfoxideand 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfoxide. Examples of thedihydroxydiaryl sulfones include 4,4′-dihydroxydiphenyl sulfone and4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone.

An example of the dihydroxydiphenyls is 4,4′-dihydroxydiphenyl. Examplesof the dihydroxydiarylfluorenes include 9,9-bis(4-hydroxyphenyl)fluoreneand 9,9-bis(4-hydroxy-3-methylphenyl)fluorene. Examples of thedihydroxydiaryladamantanes include 1,3-bis(4-hydroxyphenyl)adamantane,2,2-bis(4-hydroxyphenyl)adamantane, and1,3-bis(4-hydroxyphenyl)-5,7-dimethyladamantane.

Examples of dihydric phenols except those described above include4,4′-[1,3-phenylenebis(1-methylethylidene)]bisphenol,10,10-bis(4-hydroxyphenyl)-9-anthrone, and1,5-bis(4-hydroxyphenylthio)-2,3-dioxapentane.

In order to adjust the molecular weight of the PC-POS copolymer to beobtained, a terminal stopper (molecular weight modifier) may be used.Examples of the terminal stopper may include monohydric phenols, such asphenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol,p-nonylphenol, m-pentadecylphenol, and p-tert-amylphenol. Thosemonohydric phenols may be used alone or in combination thereof.

After the interfacial polycondensation reaction, the PC-POS copolymer(A) may be obtained by appropriately leaving the resultant at rest toseparate the resultant into an aqueous phase and an organic solventphase [separating step], washing the organic solvent phase (preferablywashing the phase with a basic aqueous solution, an acidic aqueoussolution, and water in the stated order) [washing step], concentratingthe resultant organic phase [concentrating step], and drying theconcentrated phase [drying step].

The polycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer in thefirst embodiment of the present invention by gel permeationchromatography are required to satisfy the expression (F1a):15≤wM1  (F1a)wherein wM1 represents the average content (mass %) of thepolyorganosiloxane blocks (A-2) in polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using apolycarbonate as a conversion reference of from 56,000 or more to200,000 or less among polycarbonate-polyorganosiloxane copolymersobtained through separation of the polycarbonate-polyorganosiloxanecopolymer by gel permeation chromatography.

Specifically, the average content of the polyorganosiloxane blocks (A-2)in the polycarbonate-polyorganosiloxane copolymers each having amolecular weight determined by using the polycarbonate as a conversionreference of from 56,000 or more to 200,000 or less among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation by the gel permeation chromatography is 15 mass % or more,preferably 20 mass % or more, more preferably 30 mass % or more, stillmore preferably 40 mass % or more from the viewpoint of the impactresistance of the copolymer.

In addition, the polycarbonate-polyorganosiloxane copolymers obtainedthrough the separation of the above-mentionedpolycarbonate-polyorganosiloxane copolymer by the gel permeationchromatography more desirably satisfy the following expression (F1a′):13≤wM2  (F1a′)wherein wM2 represents the average content (mass %) of thepolyorganosiloxane blocks (A-2) in polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using thepolycarbonate as a conversion reference of from 16,000 or more to lessthan 56,000 among the polycarbonate-polyorganosiloxane copolymersobtained through the separation of the polycarbonate-polyorganosiloxanecopolymer by the gel permeation chromatography.

Specifically, the average content of the polyorganosiloxane blocks (A-2)in the polycarbonate-polyorganosiloxane copolymers each having amolecular weight determined by using the polycarbonate as a conversionreference of from 16,000 or more to less than 56,000 among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation by the gel permeation chromatography is preferably 13 mass %or more, more preferably 18 mass % or more, still more preferably 22mass % or more, particularly preferably 27 mass % or more from theviewpoint of the impact resistance.

In addition, the average content (wA) of the polyorganosiloxane blocks(A-2) in the polycarbonate-polyorganosiloxane copolymer, and the averagecontent (wM1) of the polyorganosiloxane blocks (A-2) in thepolycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 56,000 or more to 200,000 or less among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography preferably satisfy the following expression(F1b):100<wM1/wA×100  (F1b)

wherein wM1 is as described above, and wA represents the average content(mass %) of the polyorganosiloxane blocks (A-2) in thepolycarbonate-polyorganosiloxane copolymer. The value of wM1/wA×100 ismore preferably 115 or more, still more preferably 130 or more, stillfurther more preferably 145 or more, particularly preferably 160 ormore.

When the value of the wM1/wA×100 falls within the range, a large amountof the polyorganosiloxane blocks (A-2) are unevenly distributed inpolycarbonate-polyorganosiloxane copolymers each having a highermolecular weight, and hence the impact resistance can be efficientlyimproved with respect to the average content of the polyorganosiloxaneblocks (A-2) in the entirety of the polycarbonate-polyorganosiloxanecopolymer.

Further, polycarbonate-polyorganosiloxane copolymers each having ahigher molecular weight determined by using the polycarbonate as aconversion reference among the polycarbonate-polyorganosiloxanecopolymers obtained through the separation of thepolycarbonate-polyorganosiloxane copolymer by the gel permeationchromatography preferably have a higher average content of thepolyorganosiloxane blocks (A-2). Specifically, thepolycarbonate-polyorganosiloxane copolymer preferably satisfies thefollowing expression (F2) and/or the following expression (F3):wM2<wM1  (F2)wherein wM1 and wM2 are as described above;wM3<wM2  (F3)wherein wM2 is as described above, and wM3 represents the averagecontent (mass %) of the polyorganosiloxane blocks (A-2) inpolycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 4,500 or more to less than 16,000 among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography.

The expression (F2) means that the average content (wM1) of thepolyorganosiloxane blocks (A-2) in the polycarbonate-polyorganosiloxanecopolymers each having a molecular weight of from 56,000 or more to200,000 or less is larger than the average content (wM2) in thepolycarbonate-polyorganosiloxane copolymers each having a molecularweight of from 16,000 or more to less than 56,000. The expression (F3)means that the average content (wM2) of the polyorganosiloxane blocks(A-2) in the polycarbonate-polyorganosiloxane copolymers each having amolecular weight of from 16,000 or more to less than 56,000 is largerthan the average content (wM3) in the polycarbonate-polyorganosiloxanecopolymers each having a molecular weight of from 4,500 or more to lessthan 16,000.

The polycarbonate-polyorganosiloxane copolymer preferably satisfies theexpression (F2) and/or the expression (F3) because a larger amount ofthe polyorganosiloxane blocks (A-2) are unevenly distributed inpolycarbonate-polyorganosiloxane copolymers each having a highermolecular weight, and hence the impact resistance can be moreefficiently improved with respect to the average content of thepolyorganosiloxane blocks (A-2) in the entirety of thepolycarbonate-polyorganosiloxane copolymer.

The average chain length of the polyorganosiloxane blocks (A-2) in thepolycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 56,000 or more to 200,000 or less among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography preferably satisfies the following expression(F4a) from the viewpoint that higher impact resistance is obtained:50≤nM1  (F4a)wherein nM1 represents the average chain length of thepolyorganosiloxane blocks (A-2) in the polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using thepolycarbonate as a conversion reference of from 56,000 or more to200,000 or less among the polycarbonate-polyorganosiloxane copolymersobtained through the separation of the polycarbonate-polyorganosiloxanecopolymer by the gel permeation chromatography.

The nM1 is preferably 50 or more, more preferably 60 or more, still morepreferably 70 or more.

In addition, the average chain length (nA) of the polyorganosiloxaneblocks (A-2) in the polycarbonate-polyorganosiloxane copolymer, and theaverage chain length (nM1) of the polyorganosiloxane blocks (A-2) in thepolycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 56,000 or more to 200,000 or less among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography preferably satisfy the following expression(F4b):100<nM1/nA×100  (F4b)

wherein the value of nM1/nA×100 is preferably more than 100, morepreferably 105 or more, still more preferably 110 or more, still furthermore preferably 115 or more, particularly preferably 120 or more.

When the value of the nM1/nA×100 falls within the range, a large amountof the polyorganosiloxane blocks (A-2) each having a longer chain lengthare unevenly distributed in polycarbonate-polyorganosiloxane copolymerseach having a higher molecular weight, and hence the impact resistancecan be efficiently improved with respect to the average chain length ofthe polyorganosiloxane blocks (A-2) in the entirety of thepolycarbonate-polyorganosiloxane copolymer.

Further, polycarbonate-polyorganosiloxane copolymers each having ahigher molecular weight determined by using the polycarbonate as aconversion reference among the polycarbonate-polyorganosiloxanecopolymers obtained through the separation of thepolycarbonate-polyorganosiloxane copolymer by the gel permeationchromatography preferably have a longer average chain length of thepolyorganosiloxane blocks (A-2).

Specifically, the copolymer preferably satisfies the followingexpression (F5) and/or the following expression (F6):nM2<nM1  (F5)wherein nM2 represents the average chain length of thepolyorganosiloxane blocks (A-2) in polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using thepolycarbonate as a conversion reference of from 16,000 or more to lessthan 56,000 among the polycarbonate-polyorganosiloxane copolymersobtained through the separation of the polycarbonate-polyorganosiloxanecopolymer by the gel permeation chromatography;nM3<nM2  (F6)wherein nM3 represents the average chain length of thepolyorganosiloxane blocks (A-2) in polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using thepolycarbonate as a conversion reference of from 4,500 or more to lessthan 16,000 among the polycarbonate-polyorganosiloxane copolymersobtained through the separation of the polycarbonate-polyorganosiloxanecopolymer by the gel permeation chromatography.

According to the expression (F5), the average chain length of thepolyorganosiloxane blocks (A-2) in the polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using thepolycarbonate as a conversion reference of from 16,000 or more to lessthan 56,000 among the polycarbonate-polyorganosiloxane copolymersobtained through the separation of the polycarbonate-polyorganosiloxanecopolymer by the gel permeation chromatography is preferably shorterthan the average chain length of the polyorganosiloxane blocks (A-2) inthe polycarbonate-polyorganosiloxane copolymers each having a molecularweight of from 56,000 or more to 200,000 or less.

According to the expression (F6), the average chain length of thepolyorganosiloxane blocks (A-2) in the polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using thepolycarbonate as a conversion reference of from 4,500 or more to lessthan 16,000 among the polycarbonate-polyorganosiloxane copolymersobtained through the separation of the polycarbonate-polyorganosiloxanecopolymer by the gel permeation chromatography is preferably shorterthan the average chain length of the polyorganosiloxane blocks (A-2) inthe polycarbonate-polyorganosiloxane copolymers each having a molecularweight of from 16,000 or more to less than 56,000.

That is, a large amount of the polyorganosiloxane blocks (A-2) eachhaving a longer chain length are unevenly distributed inpolycarbonate-polyorganosiloxane copolymers each having a highermolecular weight. Accordingly, the impact resistance can be moreefficiently improved with respect to the average chain length of thepolyorganosiloxane blocks (A-2) in the entirety of thepolycarbonate-polyorganosiloxane copolymer.

The polycarbonate-polyorganosiloxane copolymers each having a molecularweight determined by using the polycarbonate as a conversion referenceof from 56,000 or more to 200,000 or less among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography preferably satisfy the following expression(F7a):1.5≤iPOS/iPC  (F7a)

wherein iPOS represents the average content (mol) of linking groups ofthe polycarbonate blocks (A-1) and the polyorganosiloxane blocks (A-2),and iPC represents the average content (mol) of terminal groups of thepolycarbonate blocks (A-1).

In addition, iA (iPOS/iPC) serving as the ratio of iPOS to iPC in thepolycarbonate-polyorganosiloxane copolymer, and iM1 (iPOS/iPC) servingas the ratio of iPOS to iPC in the polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using thepolycarbonate as a conversion reference of from 56,000 or more to200,000 or less among the polycarbonate-polyorganosiloxane copolymersobtained through the separation of the polycarbonate-polyorganosiloxanecopolymer by the gel permeation chromatography preferably satisfy thefollowing expression (F7b):100<iM1/iA×100  (F7b)

wherein the value of iM1/iA×100 is preferably more than 100, morepreferably 130 or more, still more preferably 150 or more, still furthermore preferably 200 or more, particularly preferably 250 or more.

When the value of the iM1/iA×100 falls within the range, a large amountof molecular chains formed of the polyorganosiloxane blocks (A-2) areunevenly distributed in polycarbonate-polyorganosiloxane copolymers eachhaving a higher molecular weight, and hence the impact resistance can beefficiently improved with respect to the average number of the molecularchains formed of the polyorganosiloxane blocks (A-2) in the entirety ofthe polycarbonate-polyorganosiloxane copolymer.

Further, polycarbonate-polyorganosiloxane copolymers each having ahigher molecular weight determined by using the polycarbonate as aconversion reference among the polycarbonate-polyorganosiloxanecopolymers obtained through the separation of thepolycarbonate-polyorganosiloxane copolymer by the gel permeationchromatography preferably have a higher value of the iPOS/iPC.

Specifically, the polycarbonate-polyorganosiloxane copolymer preferablysatisfies the following expression (F8) and/or the following expression(F9):iM2<iM1  (F8)wherein iM1 is as described above, and iM2 represents the ratio(iPOS/iPC) of iPOS to iPC in polycarbonate-polyorganosiloxane copolymerseach having a molecular weight determined by using the polycarbonate asa conversion reference of from 16,000 or more to less than 56,000 amongthe polycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography;iM3<iM2  (F9)wherein iM2 is as described above, and iM3 represents the ratio(iPOS/iPC) of iPOS to iPC in polycarbonate-polyorganosiloxane copolymerseach having a molecular weight determined by using the polycarbonate asa conversion reference of from 4,500 or more to less than 16,000 amongthe polycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography.

The polycarbonate-polyorganosiloxane copolymer preferably satisfies theexpression (F8) and/or the expression (F9) because a larger amount ofmolecular chains formed of the polyorganosiloxane blocks (A-2) areunevenly distributed in polycarbonate-polyorganosiloxane copolymers eachhaving a higher molecular weight among thepolycarbonate-polyorganosiloxane copolymers obtained through theseparation of the polycarbonate-polyorganosiloxane copolymer by the gelpermeation chromatography, and hence the impact resistance can be moreefficiently improved with respect to the average number of the molecularchains formed of the polyorganosiloxane blocks (A-2) in the entirety ofthe polycarbonate-polyorganosiloxane copolymer.

<Polycarbonate-Based Resin Composition>

A polycarbonate-based resin composition according to a second embodimentof the present invention comprises: the polycarbonate-polyorganosiloxanecopolymer (A); an aromatic polycarbonate-based resin (B) except thepolycarbonate-polyorganosiloxane copolymer (A); and a polyester-basedresin (C), wherein the polyester-based resin (C) is blended with respectto 100 parts by mass of a total of the polycarbonate-polyorganosiloxanecopolymer (A) and the aromatic polycarbonate-based resin (B), andwherein a ratio of the polycarbonate-polyorganosiloxane copolymer (A)and the aromatic polycarbonate-based resin (B) in 100 mass % of a totalamount of the polycarbonate-polyorganosiloxane copolymer (A) and thearomatic polycarbonate-based resin (B), and the polyester-based resin(C) is from 50 mass % or more to 99 mass % or less:

wherein R¹ and R² each independently represent a halogen atom, an alkylgroup having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6carbon atoms, X represents a single bond, an alkylene group having 1 to8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, acycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene grouphaving 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene grouphaving 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15carbon atoms, —S—, —SO—, —SO₂—, —O—, or —CO—, R³ and R⁴ eachindependently represent a hydrogen atom, a halogen atom, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,or an aryl group having 6 to 12 carbon atoms, and “a” and “b” eachindependently represent an integer of from 0 to 4.

In the polycarbonate-based resin composition, the content of thepolycarbonate-polyorganosiloxane copolymer (A) in the total amount ofthe polycarbonate-polyorganosiloxane copolymer (A) and the aromaticpolycarbonate-based resin (B) is typically 0.1 mass % or more,preferably 1 mass % or more, more preferably 3 mass % or more, stillmore preferably 10 mass % or more, and is typically 99.9 mass % or less,preferably 99 mass % or less, more preferably 30 mass % or less, stillmore preferably 25 mass % or less, particularly preferably 20 mass % orless, most preferably 16 mass % or less from the viewpoint that a resincomposition having desired properties, such as impact resistance andchemical resistance, is obtained.

The content of the aromatic polycarbonate-based resin (B) with respectto the total amount of the polycarbonate-polyorganosiloxane copolymer(A) and the aromatic polycarbonate-based resin (B) is typically 0.1 mass% or more, preferably 1 mass % or more, more preferably 50 mass % ormore, still more preferably 80 mass % or more, and is typically 99.9mass % or less, preferably 99 mass % or less, more preferably 98 mass %or less, still more preferably 95 mass % or less, particularlypreferably 90 mass % or less from the viewpoint of the impact resistanceof the resin composition to be obtained.

In one aspect of this embodiment, the total amount of thepolycarbonate-polyorganosiloxane copolymer (A) and the aromaticpolycarbonate-based resin (B) is 100 mass %.

In this embodiment, the mass ratio “(A)/(B)” of thepolycarbonate-polyorganosiloxane copolymer (A) to the aromaticpolycarbonate-based resin (B) is typically from 0.1/99.9 to 99.9/0.1,preferably from 1/99 to 99/1, more preferably from 2/98 to 50/50, stillmore preferably from 5/95 to 20/80 from the viewpoint of the impactresistance of the resin composition to be obtained.

The content of the polyorganosiloxane blocks (A-2) in apolycarbonate-based resin formed of the polycarbonate-polyorganosiloxanecopolymer (A) and the aromatic polycarbonate-based resin (B) ispreferably 0.1 mass % or more, more preferably 0.4 mass % or more, stillmore preferably 0.8 mass % or more, still further more preferably 1 mass% or more, particularly preferably 3 mass % or more, and is preferably10 mass % or less, more preferably 7 mass % or less, still morepreferably 6 mass % or less, particularly preferably 5 mass % or less,most preferably 4 mass % or less. When the content of thepolyorganosiloxane blocks (A-2) in the polycarbonate-based resin fallswithin the range, an excellent impact-resisting characteristic can beobtained.

The viscosity-average molecular weight (Mv) of the polycarbonate-basedresin formed of the polycarbonate-polyorganosiloxane copolymer (A) andthe aromatic polycarbonate-based resin (B) may be appropriately adjustedby using, for example, a molecular weight modifier (terminal stopper) soas to be a target molecular weight in accordance with applications orproducts in which the polycarbonate-based resin is used. Theviscosity-average molecular weight of the polycarbonate-based resinformed of the polycarbonate-polyorganosiloxane copolymer (A) and thearomatic polycarbonate-based resin (B) is preferably 9,000 or more, morepreferably 12,000 or more, still more preferably 14,000 or more,particularly preferably 16,000 or more, and is preferably 50,000 orless, more preferably 30,000 or less, still more preferably 23,000 orless, particularly preferably 21,000 or less. When the viscosity-averagemolecular weight is 9,000 or more, a sufficient strength of a moldedarticle can be obtained. When the viscosity-average molecular weight is50,000 or less, injection molding or extrusion molding can be performedat the temperature at which the heat deterioration of thepolycarbonate-based resin does not occur.

The viscosity-average molecular weight (Mv) is a value calculated fromthe following Schnell's equation by measuring the limiting viscosity [r]of a methylene chloride solution at 20° C.[η]=1.23×10⁻⁵ ×Mv ^(0.83)<(B) Aromatic Polycarbonate-Based Resin>

The aromatic polycarbonate-based resin (B) except thepolycarbonate-polyorganosiloxane copolymer (A) includes, in a main chainthereof, a repeating unit represented by the following general formula(III). The polycarbonate-based resin is not particularly limited, andvarious known polycarbonate-based resins may each be used.

wherein R³⁰ and R³¹ each independently represent a halogen atom, analkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6carbon atoms, X′ represents a single bond, an alkylene group having 1 to8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, acycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene grouphaving 5 to 15 carbon atoms, —S—, —SO—, —SO₂—, —O—, or —CO—, and “d” and“e” each independently represent an integer of from 0 to 4.

Specific examples of R³⁰ and R³¹ include the same examples as those ofR¹ and R², and preferred examples thereof are also the same as those ofR¹ and R². R³⁰ and R³¹ each more preferably represent an alkyl grouphaving 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbonatoms. Specific examples of X′ include the same examples as those of X,and preferred examples thereof are also the same as those of X. “d” and“e” each independently represent preferably from 0 to 2, more preferably0 or 1.

Specifically, a resin obtained by a conventional production method for apolycarbonate may be used as the aromatic polycarbonate-based resin (B).Examples of the conventional method include: an interfacialpolymerization method involving causing the dihydric phenol-basedcompound and phosgene to react with each other in the presence of anorganic solvent inert to the reaction and an aqueous alkali solution,adding a polymerization catalyst, such as a tertiary amine or aquaternary ammonium salt, to the resultant, and polymerizing themixture; and a pyridine method involving dissolving the dihydricphenol-based compound in pyridine or a mixed solution of pyridine and aninert solvent, and introducing phosgene to the solution to directlyproduce the resin.

A molecular weight modifier (terminal stopper), a branching agent, orthe like is used as required in the reaction.

The dihydric phenol-based compound is, for example, a compoundrepresented by the following general formula (III′):

wherein R³⁰, R³¹, X′, “d”, and “e” are as defined above, and preferredexamples thereof are also the same as those described above.

Specific examples of the dihydric phenol-based compound may includethose described above in the method of producing thepolycarbonate-polyorganosiloxane copolymer (A), and preferred examplesthereof are also the same as those described above. Among them,bis(hydroxyphenyl)alkane-based dihydric phenols are preferred, andbisphenol A is more preferred.

The aromatic polycarbonate-based resins may be used alone or incombination thereof. The aromatic polycarbonate resin (B) may have astructure free of such a polyorganosiloxane block as represented by theformula (II) unlike the polycarbonate-polyorganosiloxane copolymer (A).For example, the aromatic polycarbonate-based resin (B) may be ahomopolycarbonate resin.

<Polyester-Based Resin (C)>

The polyester-based resin (C) to be used in the polycarbonate-basedresin composition of the present invention is a polymer or copolymerobtained by a condensation reaction involving using an aromaticdicarboxylic acid or a reactive derivative thereof and a diol or anester derivative thereof as main components.

Examples of the aromatic dicarboxylic acid include terephthalic acid,isophthalic acid, o-phthalic acid, 1,5-naphthalenedicarboxylic acid,2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid,4,4′-biphenyl ether dicarboxylic acid, 4,4′-biphenylmethane dicarboxylicacid, 4,4′-biphenyl sulfone dicarboxylic acid,4,4′-biphenylisopropylidene dicarboxylic acid,1,2-bis(phenoxy)ethane-4,4′-dicarboxylic acid,2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid,4,4′-p-terphenylenedicarboxylic acid, and 2,5-pyridinedicarboxylic acid.Substituted products (e.g., alkyl group-substituted products, such as5-methylisophthalic acid) and reactive derivatives (e.g., alkyl esterderivatives, such as dimethyl terephthalate and diethyl terephthalate)thereof may also be used.

Among them, terephthalic acid and 2,6-naphthalenedicarboxylic acid, andalkyl ester derivatives thereof are more preferred, and terephthalicacid and alkyl ester derivatives thereof are particularly preferred.Those aromatic dicarboxylic acids may be used alone or in combinationthereof. One or more of, for example, aliphatic dicarboxylic acids, suchas adipic acid, azelaic acid, sebacic acid, and dodecanedioic acid, andalicyclic dicarboxylic acids, such as cyclohexane dicarboxylic acid, mayalso be used in combination with the aromatic dicarboxylic acid.

Examples of the diols each serving as a component of the polyester-basedresin (C) may include: aliphatic diols, such as ethylene glycol,diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, triethyleneglycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol,1,6-hexanediol, decamethylene glycol, and 2,2-dimethyl-1,3-propanediol;alicyclic diols, such as 1,4-cyclohexanedimethanol,1,3-cyclohexanedimethanol, cyclohexanediol, and trans- orcis-2,2,4,4-tetramethyl-1,3-cyclobutanediol; and aromatic diols, such asp-xylenediol, bisphenol A, tetrabromobisphenol A, andtetrabromobisphenol A-bis(2-hydroxyethyl ether). Substituted productsthereof may also be used.

Among them, in terms of heat resistance, dimensional stability, and thelike, an aliphatic diol is preferred, ethylene glycol, 1,4-butanediol,or 1,4-cyclohexanedimethanol is more preferred, and ethylene glycol isparticularly preferred. The diols may be used alone or in combinationthereof. In addition, one or more of long-chain diols each having amolecular weight of from 400 to 6,000, that is, for example, apolyethylene glycol, a poly-1,3-propylene glycol, and apolytetramethylene glycol may be used as diol components in combinationwith the above-mentioned diols and copolymerized therewith.

The polyester-based resin (C) may be copolymerized with ahydroxycarboxylic acid, such as parahydroxybenzoic acid, any othercarboxylic acid, or an alcohol except the above-mentioned diols, andsuch copolymerized resin may also be used in the present invention.However, the amount of such copolymerized component is preferably assmall as possible, and components derived from the aromatic dicarboxylicacid and the aliphatic diol account for preferably 80 mass % or more,more preferably 90 mass % or more of the polyester-based resin (C). Inaddition, one kind of compound accounts for preferably 80 mol % or more,more preferably 90 mol % or more of each of the aromatic dicarboxylicacid and the aliphatic diol.

The polyester-based resin (C) may be branched by introducing a smallamount of a branching agent. Although the kind of the branching agent isnot limited, examples thereof include trimesic acid, trimellitic acid,trimethylolethane, trimethylolpropane, and pentaerythritol.

Specific examples of the polyester-based resin (C) include: polyethyleneterephthalate (PET), polypropylene terephthalate, polybutyleneterephthalate (PBT), polyhexylene terephthalate, polyethylenenaphthalate (PEN), polybutylene naphthalate (PBN), andpolyethylene-1,2-bis(phenoxy)ethane-4,4′-dicarboxylate; andcopolymerized polyester-based resins, such as polyethyleneisophthalate/terephthalate and polybutylene terephthalate/isophthalate.Among them, polyethylene terephthalate, polybutylene terephthalate,polyethylene naphthalate, and polybutylene naphthalate, and mixturesthereof having balanced mechanical properties and the like may bepreferably used. The compounds preferably have, for example, a ratio“PET:PBT” of from 1:1 to 1:8 (mass ratio) when used in combination.

<Other Components>

Any other additive may be incorporated into the polycarbonate-basedresin composition of the present invention to the extent that theeffects of the present invention are not impaired. Examples of the otheradditive may include an antioxidant, a UV absorber, a release agent, areinforcing material, a filler, an elastomer for an impact resistanceimprovement, a dye, a pigment, an antistatic agent, and other resinsexcept the polycarbonate.

The polycarbonate-based resin composition of the present invention isobtained by: blending the above-mentioned respective components at theabove-mentioned ratios and various optional components to be used asrequired at appropriate ratios; and kneading the components.

In one aspect of the present invention, the total content of thecomponent (A), the component (B), and the component (C) is preferablyfrom 80 mass % to 100 mass %, more preferably from 95 mass % to 100 mass% with respect to the total amount (100 mass %) of thepolycarbonate-based resin composition.

In another aspect of the present invention, the total content of thecomponent (A), the component (B), the component (C), and theabove-mentioned other component is preferably from 90 mass % to 100 mass%, more preferably from 95 mass % to 100 mass % with respect to thetotal amount (100 mass %) of the polycarbonate-based resin composition.

The blending and the kneading may be performed by a method involvingpremixing with a typically used apparatus, such as a ribbon blender or adrum tumbler, and using, for example, a Henschel mixer, a Banbury mixer,a single-screw extruder, a twin-screw extruder, a multi-screw extruder,or a Ko-kneader. In normal cases, a heating temperature at the time ofthe kneading is appropriately selected from the range of from 240° C. ormore to 320° C. or less. An extruder, in particular a vented extruder ispreferably used in the melt-kneading.

[Molded Article]

Various molded bodies may each be produced by an injection moldingmethod, an injection compression molding method, an extrusion moldingmethod, a blow molding method, a press molding method, a vacuum moldingmethod, an expansion molding method, or the like using as a raw materialthe melt-kneaded polycarbonate-based resin composition of the presentinvention or a pellet obtained through the melt-kneading. In particular,the pellet obtained through the melt-kneading can be suitably used inthe production of injection-molded bodies by injection molding andinjection compression molding.

The molded article comprising the polycarbonate-based resin compositionof the present invention can be suitably used as, for example: a casingfor apart for electrical and electronic equipment, such as a television,a radio, a video camera, a videotape recorder, an audio player, a DVDplayer, an air conditioner, a cellular phone, a display, a computer, aregister, an electronic calculator, a copying machine, a printer, afacsimile, a communication base station, or a battery; or a part for anautomobile and a building material.

EXAMPLES

The present invention is more specifically described by way of Examples.However, the present invention is by no means limited by these Examples.In each of Examples, characteristic values and evaluation results weredetermined in the following manner.

(1) Chain Length and Content of Polydimethylsiloxane

The chain length and content of a polydimethylsiloxane were calculatedby NMR measurement from the integrated value ratio of a methyl group ofthe polydimethylsiloxane. In this description, the polydimethylsiloxaneis sometimes abbreviated as PDMS.

<Quantification Method for Chain Length of Polydimethylsiloxane>

¹H-NMR Measurement Conditions

NMR apparatus: ECA500 manufactured by JEOL Resonance Co., Ltd.

Probe: 50TH5AT/FG2

Observed range: −5 ppm to 15 ppm

Observation center: 5 ppm

Pulse repetition time: 9 sec

Pulse width: 45°

NMR sample tube: 5 φ

Sample amount: 30 mg to 40 mg

Solvent: deuterochloroform

Measurement temperature: room temperature

Number of scans: 256 times

Allylphenol-Terminated Polydimethylsiloxane

A: an integrated value of a methyl group in a dimethylsiloxane moietyobserved around δ −0.02 to δ 0.5

B: an integrated value of a methylene group in allylphenol observedaround δ 2.50 to δ 2.75

Chain length of polydimethylsiloxane=(A/6)/(B/4) Eugenol-terminatedPolydimethylsiloxane

A: an integrated value of a methyl group in a dimethylsiloxane moietyobserved around δ −0.02 to δ 0.5

B: an integrated value of a methylene group in eugenol observed around δ2.40 to δ 2.70

Chain length of polydimethylsiloxane=(A/6)/(B/4)

<Quantification Method for Content of Polydimethylsiloxane>

Quantification method for the copolymerization amount of apolydimethylsiloxane in a PTBP-terminated polycarbonate obtained bycopolymerizing an allylphenol-terminated polydimethylsiloxane.

NMR apparatus: ECA-500 manufactured by JEOL Resonance Co., Ltd.

Probe: 50TH5AT/FG2

Observed range: −5 ppm to 15 ppm

Observation center: 5 ppm

Pulse repetition time: 9 sec

Pulse width: 45°

Number of scans: 256 times

NMR sample tube: 5 φ

Sample amount: 30 mg to 40 mg

Solvent: deuterochloroform

Measurement temperature: room temperature

A: an integrated value of a methyl group in a BPA moiety observed aroundδ 1.5 to δ 1.9

B: an integrated value of a methyl group in a dimethylsiloxane moietyobserved around δ −0.02 to δ 0.3

C: an integrated value of a butyl group in a p-tert-butylphenyl moietyobserved around δ 1.2 to δ 1.4

a=A/6

b=B/6

c=C/9

T=a+b+c

f=a/T×100

g=b/T×100

h=c/T×100

TW=f×254+g×74.1+h×149

PDMS (wt %)=g×74.1/TW×100

(2) Viscosity-Average Molecular Weight

A viscosity-average molecular weight (Mv) was calculated from thefollowing equation (Schnell's equation) by using a limiting viscosity[η] determined through the measurement of the viscosity of a methylenechloride solution at 20° C. with an Ubbelohde-type viscometer.[η]=1.23×10⁻⁵ ×Mv ^(0.83)(3) Gel Permeation Chromatography (GPC)

The GPC measurement of a polyorganosiloxane-polycarbonate copolymer wasperformed under the following conditions.

Test apparatus: PU-2080 manufactured by JASCO Corporation

Solvent: tetrahydrofuran (THF)

Column: TOSOH TSK-GEL MULTIPORE HXL-M×2 and Shodex KR801

Column temperature: 40° C.

Flow rate: 1.0 mL/min

Detector: UV-2075 Plus (254 nm) manufactured by JASCO Corporation

Injection concentration: 10 mg/mL

Injection volume: 0.1 mL

Fraction collector: CHF122SC manufactured by Advantec Co., Ltd.

A standard polystyrene manufactured by Tosoh Corporation was used in theproduction of a calibration curve.

Under the above-mentioned conditions, thepolyorganosiloxane-polycarbonate copolymer was fractionated into 5fractions for respective retention times to provide fractions. Theforegoing operation was repeated 100 times.

The average content and average chain length of the polyorganosiloxaneblocks (A-2), the average content of the linking groups of thepolycarbonate blocks (A-1) and the polyorganosiloxane blocks (A-2), andthe average content of the terminal groups of the polycarbonate blocks(A-1) were determined by the above-mentioned ¹H-NMR measurement for eachof the resultant fractions.

In the GPC measurement, in a region corresponding to a molecular weightdetermined by using a polycarbonate as a conversion reference of from360 or more to 1,300 or less, a cyclic organosiloxane is detected, andhence the average content and average chain length of thepolyorganosiloxane blocks (A-2) apparently seem to be high.

<Production of Polycarbonate Oligomer>

Sodium dithionite was added in an amount of 2,000 ppm with respect tobisphenol A (BPA) (to be dissolved later) to 5.6 mass % aqueous sodiumhydroxide, and then BPA was dissolved in the mixture so that theconcentration of BPA was 13.5 mass %. Thus, a solution of BPA in aqueoussodium hydroxide was prepared. The solution of BPA in aqueous sodiumhydroxide, methylene chloride, and phosgene were continuously passedthrough a tubular reactor having an inner diameter of 6 mm and a tubelength of 30 m at flow rates of 40 L/hr, 15 L/hr, and 4.0 kg/hr,respectively. The tubular reactor had a jacket portion and thetemperature of the reaction liquid was kept at 40° C. or less by passingcooling water through the jacket. The reaction liquid that had exitedthe tubular reactor was continuously introduced into a baffled vesseltype reactor provided with a sweptback blade and having an internalvolume of 40 L. The solution of BPA in aqueous sodium hydroxide, 25 mass% aqueous sodium hydroxide, water, and a 1 mass % aqueous solution oftriethylamine were further added to the reactor at flow rates of 2.8L/hr, 0.07 L/hr, 17 L/hr, and 0.64 L/hr, respectively, to perform areaction. An aqueous phase was separated and removed by continuouslytaking out the reaction liquid overflowing the vessel type reactor andleaving the reaction liquid at rest. Then, a methylene chloride phasewas collected.

The polycarbonate oligomer thus obtained had a concentration of 341 g/Land a chloroformate group concentration of 0.71 mol/L.

Production Example 1

<PC-POS Copolymer (A-1a)>

Values for the following (i) to (xiv) are as shown in Table 1.

(i) L of the polycarbonate oligomer solution (PCO) produced as describedabove, (ii) L of methylene chloride (MC), a solution obtained bydissolving (iv) g of an allylphenol terminal-modifiedpolydimethylsiloxane having an average chain length “n” of (iii) in (v)L of methylene chloride (MC), and (vi) mL of triethylamine (TEA) wereloaded into a 50 L vessel-type reactor including a baffle board, apaddle-type stirring blade, and a cooling jacket. (vii) g of 6.4 mass %aqueous sodium hydroxide (NaOHaq) was added to the mixture understirring, and a reaction between the polycarbonate oligomer and theallylphenol terminal-modified PDMS was performed for 20 minutes.

A solution of p-tert-butylphenol (PTBP) in methylene chloride (obtainedby dissolving (viii) g of PTBP in (ix) L of methylene chloride (MC)) anda solution of BPA in aqueous sodium hydroxide (obtained by dissolving(xiii) g of BPA in an aqueous solution obtained by dissolving (x) g ofNaOH and (xi) g of sodium dithionite (Na₂S₂O₄) in (xii) L of water) wereadded to the polymerization liquid, and the mixture was subjected to apolymerization reaction for 40 minutes.

(xiv) L of methylene chloride (MC) was added to the resultant fordilution, and the mixture was stirred for 10 minutes. After that, themixture was separated into an organic phase containing a PC-POS, and anaqueous phase containing excess amounts of BPA and NaOH, and the organicphase was isolated.

A solution of the PC-POS in methylene chloride thus obtained wassequentially washed with 0.03 mol/L aqueous NaOH and 0.2 mol/Lhydrochloric acid in amounts of 15 vol % each with respect to thesolution. Next, the solution was repeatedly washed with pure water untilan electric conductivity in an aqueous phase after the washing became0.01 μS/m or less.

The solutions of the polycarbonates in methylene chloride obtained bythe washing were concentrated and pulverized, and the resultant flakeswere dried under reduced pressure at 120° C. to provide PC-POScopolymers (A1) to (A17). The resultant flake was subjected to thefollowing various kinds of measurement: PDMS content measurement,unreacted PDMS amount measurement, viscosity-average molecular weightmeasurement, and measurement by GPC. The value of the iM1 of the flakewas 3.2, the value of the iM2 thereof was 2.3, the value of the iM3thereof was 0.7, and the value of the iM1/iA×100 thereof was 287. Theother results are shown in Table 1.

TABLE 1 Production Production Example 1 Example 2 PC-POS (A) A-1a A-1b(i) PCO (L) 11 11 (ii) MC (L) 24.5 24.5 (iii) PDMS chain length (n) 6188 (iv) PDMS loading amount (g) 1,800 1,400 (v) MC (L) 2.0 2.0 (vi) TEA(mL) 6.2 6.2 (vii) NaOHaq (g) 1,405 937 (viii) PTBP (g) 107.6 107.6 (ix)MC (L) 0.5 0.5 (x) NaOH (g) 412 412 (xi) Na₂S₂O₄ (g) 1.5 1.5 (xii) Water(L) 6.0 6.0 (xiii) BPA (g) 766 766 (xiv) MC (L) 0 0 PDMS content (wt %)30 25 Unreacted PDMS amount (ppm) ≤150 ≤150 Mv 17,700 17,700 wM1 (mass%) 48 41 wM2 (mass %) 30 36 wM3 (mass %) 21 23 wM1/wA × 100 175 167 nM176 122 nM2 62 106 nM3 52 84 nM1/nA × 100 125 131

Production Example 2

<PC-POS Copolymer (A-1b)>

Production and measurement were performed in the same manner as inProduction Example 1 except that the values (i) to (xiv) were changed asdescribed in Table 1 shown above.

<PC-POS Copolymer (A-2)>

PC-POS copolymer A-2a: “FG1700” [PC-POS copolymer, polyorganosiloxaneblock chain length: 88, polyorganosiloxane content: 6 mass %,viscosity-average molecular weight Mv: 17,700]

<Aromatic Polycarbonate-Based Resin (B)>

Aromatic polycarbonate-based resin B-1: “FN2500” [viscosity-averagemolecular weight Mv: 23,500]

Aromatic polycarbonate-based resin B-2: “FN2200” [viscosity-averagemolecular weight Mv: 21,300]

Aromatic polycarbonate-based resin B-3: “FN1900” [viscosity-averagemolecular weight Mv: 19,300]

Aromatic polycarbonate-based resin B-4: “FN1700” [viscosity-averagemolecular weight Mv: 17,700]

<Polyester-Based Resin (C)>

Polyethylene terephthalate: “J055” [manufactured by Mitsui Chemicals,Inc.]

Polyethylene terephthalate: “KS760K-12” [manufactured by Kuraray Co.,Ltd.]

Polybutyleneterephthalate: “1401X06” [manufactured by Toray Industries,Inc.]

Polybutylene terephthalate: “DURANEX 2002 EF2001N” [manufactured byPolyplastics Co., Ltd.]

<Other Component>

Antioxidant: “IRGAFOS 168 (product name)” [tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Japan]

Antioxidant: “IRGANOX 1076 (product name)” [octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASFJapan]

Examples a and b, Examples 1 to 23, and Comparative Examples 1 to 21

The PC-POS copolymers A-1a and A-1b obtained in Production Examples 1and 2, and the other respective components were mixed at blending ratiosshown in Table 2 to Table 6. Each of the mixtures was supplied to avented twin-screw extruder (manufactured by Toshiba Machine Co., Ltd.,TEM-35B), and was melt-kneaded at a screw revolution number of 150 rpm,an ejection amount of 20 kg/hr, and a resin temperature of from 278° C.to 300° C. to provide an evaluation pellet sample. The compositions andevaluation items of PC-based resin compositions are shown in Table 2 toTable 6.

TABLE 2 Example Example Example Example Comparative Comparative ExampleExample a b 1 2 Example 1 Example 2 3 4 A-1 A-1a (Production parts bymass 8 15 12 Example 1) A-1b (Production parts by mass 9.6 18 14.4Example 2) A-2 FG1700 parts by mass 75 B B-1 (FN2500) parts by mass 1515 B-2 (FN2200) parts by mass B-3 (FN1900) parts by mass B-4 (FN1700)parts by mass 92 90.4 60 57 75 48 45.6 C J055 parts by mass 25 25 25 2525 25 KS760K-12 parts by mass 1401X06 parts by mass Other Irgafos 168parts by mass 0.05 0.05 0.10 0.10 0.10 0.10 0.10 0.10 Irganox 1076 partsby mass 0.10 0.10 0.10 0.10 0.10 0.10 Polyorganosiloxane block mass %2.4 2.4 6.0 6.0 6.0 0.0 4.8 4.8 content in PC-based resin [(A) + (B)]Viscosity-average molecular — 17,700 17,700 17,700 17,700 17,700 17,70018,900 18,900 weight (Mv) of PC-based resin [(A) + (B)] MFR (300° C.,1.2 kg) g/10 min — — 13 13 13 21 12 11 Q value (280° C., 160 kg) ×0.01ml/s 13 13 11 11 11 11 11 10 Izod impact strength (23° C.) kJ/m² 73 7496 92 91 11 97 99 Izod impact strength (0° C.) kJ/m² — — — — — — — —Izod impact strength (−10° C.) kJ/m² — — 84 83 80 9 83 79 Izod impactstrength (−20° C.) kJ/m² — — 74 70 29 9 74 31 Izod impact strength (−30°C.) kJ/m² — — 31 23 19 8 24 19 Izod impact strength (−40° C.) kJ/m² 5453 — — — — — — Deflection temperature under ° C. 128 128 117 118 117 122120 120 load Chemical resistance to isobutyl acetate A A A B A AChemical resistance to toluene A A B B A A Chemical resistance toheptane A A A A A A Comparative Comparative Example Example ComparativeComparative Example 3 Example 4 5 6 Example 5 Example 6 A-1 A-1a(Production parts by mass 7.5 Example 1) A-1b (Production parts by mass9 Example 2) A-2 FG1700 parts by mass 60 37.5 B B-1 (FN2500) parts bymass 15 37.5 37.5 37.5 B-2 (FN2200) parts by mass 43 B-3 (FN1900) partsby mass 57 32 B-4 (FN1700) parts by mass 18 30 28.5 C J055 parts by mass25 25 25 25 25 25 KS760K-12 parts by mass 1401X06 parts by mass OtherIrgafos 168 parts by mass 0.10 0.10 0.10 0.10 0.10 0.10 Irganox 1076parts by mass 0.10 0.10 0.10 0.10 0.10 0.10 Polyorganosiloxane blockmass % 4.8 0.0 3.0 3.0 3.0 0.0 content in PC-based resin [(A) + (B)]Viscosity-average molecular — 18,900 18,900 20,600 20,600 20,600 20,400weight (Mv) of PC-based resin [(A) + (B)] MFR (300° C., 1.2 kg) g/10 min11 17 10 11 10 13 Q value (280° C., 160 kg) ×0.01 ml/s 10 10 7.6 7.9 6.87.7 Izod impact strength (23° C.) kJ/m² 97 61 97 101 104 82 Izod impactstrength (0° C.) kJ/m² — 10 93 96 89 10 Izod impact strength (−10° C.)kJ/m² 76 9 77 57 22 10 Izod impact strength (−20° C.) kJ/m² 13 9 20 18 —9 Izod impact strength (−30° C.) kJ/m² 16 — 15 14 13 — Izod impactstrength (−40° C.) kJ/m² — — — — — — Deflection temperature under ° C.119 123 122 122 121 124 load Chemical resistance to isobutyl acetate A BA A A B Chemical resistance to toluene A B A A A A Chemical resistanceto heptane A A A A A A

TABLE 3 Example Comparative Example Example Comparative 7 Example 7 8 9Example 8 A-1 A-1a (Production parts by mass 12 7.5 Example 1) A-1b(Production parts by mass 9 Example 2) A-2 FG1700 parts by mass 60 B B-1(FN2500) parts by mass 15 15 37.5 37.5 37.5 B-2 (FN2200) parts by massB-3 (FN1900) parts by mass B-4 (FN1700) parts by mass 48 30 28.5 37.5 CJ055 parts by mass KS760K-12 parts by mass 25 25 25 25 25 1401X06 partsby mass Other Irgafos 168 parts by mass 0.10 0.10 0.10 0.10 0.10 Irganox1076 parts by mass 0.10 0.10 0.10 0.10 0.10 Polyorganosiloxane blockmass % 4.8 4.8 3.0 3.0 3.0 content in PC-based resin [(A) + (B)]Viscosity-average molecular — 18,900 18,900 20,600 20,600 20,600 weight(Mv) of PC-based resin [(A) + (B)] MFR (300° C., 1.2 kg) g/10 min 14 1413 13 12 Q value (280° C., 160 kg) ×0.01 ml/s 12 12 11 10 10 Izod impactstrength (23° C.) kJ/m² 79 79 92 91 88 Izod impact strength (0° C.)kJ/m² 60 20 74 32 16 Izod impact strength (−10° C.) kJ/m² 25 16 18 16 13Izod impact strength (−20° C.) kJ/m² — — — — — Izod impact strength(−30° C.) kJ/m² — — — — — Izod impact strength (−40° C.) kJ/m² — — — — —Deflection temperature under ° C. 119 118 121 121 120 load Chemicalresistance to isobutyl acetate A A A A A Chemical resistance to tolueneA A A A A Chemical resistance to heptane A A A A A Example ExampleComparative Comparative 10 11 Example 9 Example 10 A-1 A-1a (Productionparts by mass 13.6 Example 1) A-1b (Production parts by mass 16.3Example 2) A-2 FG1700 parts by mass 68 B B-1 (FN2500) parts by mass 1717 17 B-2 (FN2200) parts by mass B-3 (FN1900) parts by mass 62 B-4(FN1700) parts by mass 54.4 51.7 23 C J055 parts by mass 15 15 15 15KS760K-12 parts by mass 1401X06 parts by mass Other Irgafos 168 parts bymass 0.10 0.10 0.10 0.10 Irganox 1076 parts by mass 0.10 0.10 0.10 0.10Polyorganosiloxane block mass % 4.8 4.8 4.8 0.0 content in PC-basedresin [(A) + (B)] Viscosity-average molecular — 18,900 18,900 18,90018,900 weight (Mv) of PC-based resin [(A) + (B)] MFR (300° C., 1.2 kg)g/10 min 12 11 13 18 Q value (280° C., 160 kg) ×0.01 ml/s 9 9 11 9 Izodimpact strength (23° C.) kJ/m² 90 89 88 89 Izod impact strength (0° C.)kJ/m² — — — — Izod impact strength (−10° C.) kJ/m² — — — — Izod impactstrength (−20° C.) kJ/m² 88 82 75 10 Izod impact strength (−30° C.)kJ/m² 85 77 64 10 Izod impact strength (−40° C.) kJ/m² 69 59 24 9Deflection temperature under ° C. 123 123 121 126 load Chemicalresistance to isobutyl acetate A A A B Chemical resistance to toluene AA B B Chemical resistance to heptane A A A A

TABLE 4 Example Example Comparative Comparative Example ExampleComparative 12 13 Example 11 Example 12 14 15 Example 13 A-1 A-1a(Production parts by mass 15.2 13.6 Example 1) A-1b (Production parts bymass 18.2 16.3 Example 2) A-2 FG1700 parts by mass 76 68 B B-1 (FN2500)parts by mass 19 19 19 17 17 17 B-2 (FN2200) parts by mass B-3 (FN1900)parts by mass 70 B-4 (FN1700) parts by mass 60.8 57.8 25 54.4 51.7 CJ055 parts by mass 5 5 5 5 KS760K-12 parts by mass 1401X06 parts by mass15 15 15 Other Irgafos 168 parts by mass 0.10 0.10 0.10 0.10 0.10 0.100.10 Irganox 1076 parts by mass 0.10 0.10 0.10 0.10 0.10 0.10 0.10Polyorganosiloxane block mass % 4.8 4.8 4.8 0.0 4.8 4.8 4.8 content inPC-based resin [(A) + (B)] Viscosity-average molecular — 18,900 18,90018,900 18,900 18,900 18,900 18,900 weight (Mv) of PC-based resin [(A) +(B)] MFR (300° C., 1.2 kg) g/10 min 12 12 12 20 42 37 41 Q value (280°C., 160 kg) ×0.01 ml/s 10 10 10 10 29 24 28 Izod impact strength (23°C.) kJ/m² 84 84 84 82 94 103 95 Izod impact strength (0° C.) kJ/m² — — —54 81 96 85 Izod impact strength (−10° C.) kJ/m² — — — 15 80 87 72 Izodimpact strength (−20° C.) kJ/m² — — — — 66 71 20 Izod impact strength(−30° C.) kJ/m² 79 73 73 11 20 20 16 Izod impact strength (−40° C.)kJ/m² 79 70 69 10 — — — Deflection temperature under ° C. 125 125 124128 102 102 102 load Chemical resistance to Presence or A A A B A A Aisobutyl acetate absence of breakage Whitening B B B B B B B Chemicalresistance to Presence or A A A A A A A heptane absence of crackComparative Example Example Comparative Comparative Example 14 16 17Example 15 Example 16 A-1 A-1a (Production parts by mass 15.2 Example 1)A-1b (Production parts by mass 18.2 Example 2) A-2 FG1700 parts by mass76 B B-1 (FN2500) parts by mass 19 19 19 B-2 (FN2200) parts by mass B-3(FN1900) parts by mass 62 70 B-4 (FN1700) parts by mass 23 60.8 57.8 25C J055 parts by mass KS760K-12 parts by mass 1401X06 parts by mass 15 55 5 5 Other Irgafos 168 parts by mass 0.10 0.10 0.10 0.10 0.10 Irganox1076 parts by mass 0.10 0.10 0.10 0.10 0.10 Polyorganosiloxane blockmass % 0.0 4.8 4.8 4.8 0.0 content in PC-based resin [(A) + (B)]Viscosity-average molecular — 18,900 18,900 18,900 18,900 18,900 weight(Mv) of PC-based resin [(A) + (B)] MFR (300° C., 1.2 kg) g/10 min 43 1817 22 27 Q value (280° C., 160 kg) ×0.01 ml/s 21 13 13 15 14 Izod impactstrength (23° C.) kJ/m² 7 86 87 88 11 Izod impact strength (0° C.) kJ/m²8 — — — — Izod impact strength (−10° C.) kJ/m² 7 — — — — Izod impactstrength (−20° C.) kJ/m² 8 — — — — Izod impact strength (−30° C.) kJ/m²7 75 72 69 9 Izod impact strength (−40° C.) kJ/m² — 68 67 63 9Deflection temperature under ° C. 105 118 118 117 121 load Chemicalresistance to Presence or B B B B C isobutyl acetate absence of breakageWhitening B B B B B Chemical resistance to Presence or B A A B B heptaneabsence of crack

TABLE 5 Example Example Comparative Comparative Comparative 18 19Example 17 Example 18 Example 19 A-1 A-1a (Production parts by mass 7.5Example 1) A-1b (Production parts by mass 9 Example 2) A-2 FG1700 partsby mass 37.5 80 B B-1 (FN2500) parts by mass 37.5 37.5 37.5 20 B-2(FN2200) parts by mass 43 B-3 (FN1900) parts by mass 32 B-4 (FN1700)parts by mass 30 28.5 C J055 parts by mass KS760K-12 parts by mass1401X06 parts by mass 25 25 25 25 Other Irgafos 168 parts by mass 0.100.10 0.10 0.10 0.10 Irganox 1076 parts by mass 0.10 0.10 0.10 0.10 0.10Polyorganosiloxane block mass % 3.0 3.0 3.0 0.0 4.8 content in PC-basedresin [(A) + (B)] Viscosity-average molecular — 20,600 20,600 20,60020,400 18,900 weight (Mv) of PC-based resin [(A) + (B)] MFR (300° C.,1.2 kg) g/10 min 65 74 65 70 12 Q value (280° C., 160 kg) ×0.01 ml/s 2525 36 33 10 Izod impact strength (23° C.) kJ/m² 80 81 80 6 79 Izodimpact strength (0° C.) kJ/m² — — — 7 76 Izod impact strength (−10° C.)kJ/m² 12 13 13 7 73 Izod impact strength (−20° C.) kJ/m² 11 12 12 7 72Izod impact strength (−30° C.) kJ/m² — — — — 70 Izod impact strength(−40° C.) kJ/m² — — — — 68 Deflection temperature under ° C. 90 91 91 91127 load Chemical resistance to isobutyl acetate A A A B C Chemicalresistance to toluene A A A A B Chemical resistance to heptane A A A B B

TABLE 6 Comparative Example Example Comparative Example Example Example20 20 21 Example 21 22 23 A-1 A-1a (Production parts by mass 12 7.5Example 1) A-1b (Production parts by mass 14.4 9 Example 2) A-2 FG1700parts by mass 60 37.5 B B-1 (FN2500) parts by mass 15 15 15 37.5 37.537.5 B-2 (FN2200) parts by mass B-3 (FN1900) parts by mass B-4 (FN1700)parts by mass 45.6 48 28.5 30 C J055 parts by mass KS760K-12 parts bymass 1401X06 parts by mass 2002 EF2001N parts by mass 25 25 25 25 25 25Other Irgafos 168 parts by mass 0.10 0.10 0.10 0.10 0.10 0.10 Irganox1076 parts by mass 0.10 0.10 0.10 0.10 0.10 0.10 Polyorganosiloxaneblock mass % 4.8 4.8 4.8 3.0 3.0 3.0 content in PC-based resin [(A) +(B)] Viscosity-average molecular — 18,900 18,900 18,900 20,600 20,60020,600 weight (Mv) of PC-based resin [(A) + (B)] MFR (300° C., 1.2 kg)g/10 min 32 29 30 29 27 28 Q value (280° C., 160 kg) x0.01 ml/s 21 19 2116 15 15 Izod impact strength (23° C.) kJ/m² 106 123 113 93 118 104 Izodimpact strength (0° C.) kJ/m² 98 111 107 14 99 97 Izod impact strength(−10° C.) kJ/m² 55 105 104 13 19 88 Izod impact strength (−20° C.) kJ/m²16 97 97 12 16 17 Izod impact strength (−30° C.) kJ/m² 15 83 88 11 15 15Izod impact strength (−40° C.) kJ/m² — — — — — — Deflection temperatureunder ° C. 88 88 86 90 89 89 load Chemical resistance to isobutylacetate A A A A A A Chemical resistance to toluene A A A A A A Chemicalresistance to heptane A A A A A A[Evaluation Test]<Fluidity Evaluation>(MFR)

The amount (g/10 min) of a molten resin flowing out of a die having adiameter of 2.095±0.005 mm and a length of 8.000±0.025 mm was measuredby using the above-mentioned pellet in conformity with JIS K 7210-1:2014at 300° C. under a load of 1.2 kg.

<Q Value (Flow Value) [Unit; 10⁻² mL/Sec]>

The amount (mL/sec) of a molten resin flowing out of a nozzle having adiameter of 1.00 mm and a length of 10.00 mm was measured by using theabove-mentioned pellet and a Koka flow tester in conformity with JIS K7210-1:2014: Appendix JA at 280° C. under a pressure of 160 kgf. A Qvalue represents an outflow amount per unit time, and a higher numericalvalue therefor means that the fluidity of the resin is better.

<Impact Resistance>

The pellet obtained in the foregoing was dried at 120° C. for 8 hours,and was then subjected to injection molding with an injection moldingmachine (manufactured by Nissei Plastic Industrial Co., Ltd., NEX110,screw diameter: 36 mmφ) at a cylinder temperature of 280° C. and a dietemperature of 80° C. to produce an Izod test piece (length: 63.5 mm,width: 12.7 mm, thickness: 3.2 mm). Notched Izod impact strengths at−40° C., −30° C., −20° C., −10° C., 0° C., and 23° C. were measured byusing a test piece obtained by making a notch (r=0.25 mm±0.05 mm) in thetest piece through post-processing in conformity with ASTM StandardD-256.

<Deflection Temperature Under Load (Unit; ° C.)>

The pellet obtained in the foregoing was dried at 120° C. for 8 hours,and was then subjected to injection molding with an injection moldingmachine (manufactured by Nissei Plastic Industrial Co., Ltd., NEX110,screw diameter: 36 mmφ) at a cylinder temperature of 280° C. and a dietemperature of 80° C. to provide a test piece (length: 127 mm, width:12.7 mm, thickness: 3.2 mm). A load of 1.8 MPa was applied to the testpiece in conformity with ASTM Standard D-648 at a rate of temperatureincrease of 120° C./h and a fulcrum-to-fulcrum distance of 100 mm, andthe temperature at which the deflection of the test piece measured in anedgewise manner reached 0.26 mm was recorded.

<Chemical Resistance to Isobutyl Acetate>

The pellet obtained in the foregoing was subjected to injection moldingat a molding temperature of 280° C. and a die temperature of 80° C. toprovide a test piece measuring 127 mm long by 12.7 mm wide by 3.2 mmthick. A strain of 1.0% was applied to the test piece by a three-pointbending test method at a span distance of 80 mm, and then isobutylacetate was applied thereto with a swab. The test piece was left tostand at 23° C. for 2 minutes, and then a change in appearance thereofwas observed, followed by an evaluation in accordance with the followingcriteria.

A case in which the sample was free of any appearance change or a finecrack occurred on its surface was indicated by Symbol “A”.

A case in which a crack arrived from the surface of the sample to theopposite surface thereof in the thickness direction thereof wasindicated by Symbol “B”.

A case in which the sample broke and hence no stress was applied theretowith a jig was indicated by Symbol “C”.

<Chemical Resistance to Toluene>

The pellet obtained in the foregoing was subjected to injection moldingat a molding temperature of 280° C. and a die temperature of 80° C. toprovide a test piece measuring 127 mm long by 12.7 mm wide by 3.2 mmthick. A strain of 1.0% was applied to the test piece by a three-pointbending test method at a span distance of 80 mm, and then two drops oftoluene was applied thereto with a pipette. The test piece was left tostand at 23° C. for 15 minutes, and then a change in appearance thereofwas observed, followed by an evaluation in accordance with the followingcriteria.

A case in which the test piece did not whiten was indicated by Symbol“A”.

A case in which the test piece whitened was indicated by Symbol “B”.

<Chemical Resistance to Heptane>

The pellet obtained in the foregoing was subjected to injection moldingat a molding temperature of 280° C. and a die temperature of 80° C. toprovide a test piece measuring 127 mm long by 12.7 mm wide by 3.2 mmthick. A strain of 1.0% was applied to the test piece by a three-pointbending test method at a span distance of 80 mm, and then a cloth wasplaced on the strained portion. Heptane was continuously dropped on thecloth at 23° C. for 30 minutes, and then a change in appearance of thetest piece was observed, followed by an evaluation in accordance withthe following criteria.

A case in which no crack occurred on the surface of the test piece wasindicated by Symbol “A”.

A case in which a crack occurred on the surface of the test piece wasindicated by Symbol “B”.

INDUSTRIAL APPLICABILITY

The polycarbonate resin obtained in the present invention can besuitably used as a casing and the like for a part for electrical andelectronic equipment, and a part and the like for an automobile and abuilding material because the resin is excellent in impact resistance.

The invention claimed is:
 1. A polycarbonate-based resin composition,comprising: a polycarbonate-polyorganosiloxane copolymer (A) comprisingpolycarbonate blocks (A-1) each formed of a repeating unit representedby the following general formula (I); and polyorganosiloxane blocks(A-2) each containing a repeating unit represented by the followinggeneral formula (II), wherein the polycarbonate-polyorganosiloxanecopolymer satisfies the following expression (F1a):15≤wM1  (F1a) wherein wM1 represents an average content (mass %) of thepolyorganosiloxane blocks (A-2) in polycarbonate-polyorganosiloxanecopolymers each having a molecular weight determined by using apolycarbonate as a conversion reference of from 56,000 or more to200,000 or less among polycarbonate-polyorganosiloxane copolymersobtained through separation of the polycarbonate-polyorganosiloxanecopolymer by gel permeation chromatography; an aromaticpolycarbonate-based resin (B) except thepolycarbonate-polyorganosiloxane copolymer (A); and a polyester-basedresin (C), wherein the polyester-based resin (C) is blended with respectto 100 parts by mass of a total of the polycarbonate-polyorganosiloxanecopolymer (A) and the aromatic polycarbonate-based resin (B), andwherein a ratio of the polycarbonate-polyorganosiloxane copolymer (A)and the aromatic polycarbonate-based resin (B) in 100 mass % of a totalamount of the polycarbonate-polyorganosiloxane copolymer (A) and thearomatic polycarbonate-based resin (B), and the polyester-based resin(C) is from 50 mass % or more to 99 mass % or less:

wherein R¹ and R² each independently represent a halogen atom, an alkylgroup having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6carbon atoms, X represents a single bond, an alkylene group having 1 to8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, acycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene grouphaving 5 to 15 carbon atoms, a fluorenediyl group, an arylalkylene grouphaving 7 to 15 carbon atoms, an arylalkylidene group having 7 to 15carbon atoms, —S—, —SO—, —SO₂—, —O—, or —CO—, R³ and R⁴ eachindependently represent a hydrogen atom, a halogen atom, an alkyl grouphaving 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms,or an aryl group having 6 to 12 carbon atoms, and “a” and “b” eachindependently represent an integer of from 0 to
 4. 2. Thepolycarbonate-polyorganosiloxane copolymer according to claim 1, whereinthe aromatic polycarbonate-based resin (B) contains a polycarbonateblock including, in a main chain thereof, a repeating unit representedby the following general formula (III):

wherein R³⁰ and R³¹ each independently represent a halogen atom, analkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6carbon atoms, X′ represents a single bond, an alkylene group having 1 to8 carbon atoms, an alkylidene group having 2 to 8 carbon atoms, acycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene grouphaving 5 to 15 carbon atoms, —S—, —SO—, —SO₂—, —O—, or —CO—, and “d” and“e” each independently represent an integer of from 0 to
 4. 3. Thepolycarbonate-based resin composition according to claim 1, wherein amass ratio “(A)/(B)” of the polycarbonate-polyorganosiloxane copolymer(A) to the aromatic polycarbonate-based resin (B) is from 0.1/99.9 to99.9/0.1.
 4. The polycarbonate-based resin composition according toclaim 1, wherein a content of the polyorganosiloxane blocks (A-2) withrespect to a total of the polycarbonate-polyorganosiloxane copolymer (A)and the aromatic polycarbonate-based resin (B) is from 0.1 mass % ormore to 10 mass % or less.
 5. The polycarbonate-based resin compositionaccording to claim 1, wherein a polycarbonate-based resin formed of thepolycarbonate-polyorganosiloxane copolymer (A) and the aromaticpolycarbonate-based resin (B) has a viscosity-average molecular weight(Mv) of from 9,000 or more to 50,000 or less.
 6. The polycarbonate-basedresin composition according to claim 1, wherein the polyester-basedresin (C) comprises at least one selected from a polyethyleneterephthalate and a polybutylene terephthalate.
 7. A molded article,which is obtained by molding the polycarbonate-based resin compositionof claim
 1. 8. The molded article according to claim 7, wherein themolded article comprises a casing for electrical and electronicequipment.
 9. The molded article according to claim 7, wherein themolded article comprises a part for an automobile and a buildingmaterial.